Marked thermoplastic compositions, methods of making and articles comprising the same, and uses thereof

ABSTRACT

An article for laser marking can comprising: a thermoplastic composition comprising a thermoplastic polymer, an active component comprising at least one of a polymeric unit and an additive, wherein the thermoplastic polymer has a visible transmission of greater than or equal to 80% according to ASTM D1003-00, Procedure A, using D65 illumination, 10 degrees observer, and thickness of 1 mm; and a mark produced by chemical rearrangement of the active component generated by a laser of a first wavelength; wherein the mark exhibits at least one of: (i) a change in optical properties in the region 400 nm to 700 nm when exposed to light having a wavelength less than or equal to 500 nm; and (ii) a change in optical properties in the region of 400 nm to 700 nm when exposed to light having a wavelength greater than or equal to the first wavelength.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a divisional of U.S. application Ser. No.13/909,378, filed Jun. 4, 2013 which is a continuation-in-part of U.S.application Ser. No. 13/487,641, filed Jun. 4, 2012, which are herebyincorporated by reference in their entirety.

TECHNICAL FIELD

The present disclosure relates to marked thermoplastic compositions andmethods of making and using the same.

BACKGROUND

A range of lasers operating at various wavelengths can be used toinscribe or mark thermoplastic compositions with text, logos, and/orother identifiers. For example, opaque thermoplastic compositions can bemarked with a 1064 nanometer (nm) laser light and rely on heat build-upin the substrate as the method of interaction between the laser lightand the thermoplastic composition. Depending on the composition and/orthe lasering parameters, the heat generated either causes a char, i.e.,carbonization, to form a dark mark, or, alternatively a swelling fromthe formation of voids just below the surface and yields a light coloredmark on a dark background, i.e., foaming. A vaporization process, or thebleaching of an additive, or a bleaching of the combination ofadditives, can also achieve light colored marks by exposing the lightercolored, thermally stable materials below the surface. The 1064 nm laseris also used to mark transparent compositions to give a dark mark.However, the inherent low levels of absorption by most thermoplastics inthis area of the electromagnetic spectrum (i.e., 500 nm to 1,200 nm) canlead to inhomogeneous interactions between the laser light and thetransparent substrate, which can lead to localized superheating and aninconsistent or poor quality mark. As a consequence, low levels ofcarbon black or other more specialized near infrared absorbing pigmentsor additives are often required in order to increase the quality andconsistency of the mark. A disadvantage of using such additives is areduction in visible transmission, increased haze and large color shiftsdue to the inherent residual color or particulate nature of theadditives.

A photochemical interaction between the substrate and the laser light isanother reaction mechanism by which identifiers are transferred tothermoplastics compositions. Lower wavelength light lasers such as thoseat 532 nm and especially with wavelengths lower than 400 nm (e.g.,ultraviolet) generate contrast in polymer compositions in such a manner.The process is often referred to as “cold marking” due to the perceptionthat there is limited thermal effect from the interaction of the laserswith the thermoplastic compositions. Ultraviolet lasers arepredominantly used to mark opaque thermoplastic compositions containingtitanium dioxide and yield a dark mark on white or light coloredsubstrates.

However, there are some problems associated with the above processes.For example, the laser is not restricted to interacting at the surfaceor upper portion of the substrate to be marked and the intense lightfrom the laser easily passes through the outer part or layer. In mostcases, it is desirable that the mark is confined to the surface or closeto the surface and that the laser beam does not interact or damage othermaterials or components beneath the layer or part to be inscribed.Exemplary designs or structures wherein the material to be marked housesdevices or overlays other materials include a two shot or over-moldedpart such as in automotive glazing, a thermoplastic screen or housingencasing electronic devices such as mobile phones. One option is theaddition of either IR absorbing additives or scattering additives, suchas titanium dioxide, to the outer material, which restricts thetransparency, haze, and colors available. Another problem is that anovert white or light colored mark is either impossible or the mark is adark brown to tan color due to the persistent contribution from thecarbonization effect and more particularly, in transparent compositionswhere a black mark is achieved due to strong carbonization of thematerial. Also, the durability of light colored marks is poor as thevoids that cause the swelling are easily compressed and it is extremelydifficult to achieve a semi-covert (i.e., barely visible) watermark,particularly in transparent compositions.

Another challenge exists when the material to be inscribed alsofunctions as the laser transparent component in an article to beassembled by laser transmission welding (LTW). In general the lasersused for LTW are based on wavelengths longer than 800 nm. In order tojoin two components by LTW one component needs to be essentially lasertransparent (e.g., no absorption), while the second component needs toabsorb the laser light. The laser light then passes through the firstcomponent and heat is generated at the interface through the absorptionof the laser light in the second component. The heat is conducted to thefirst layer, which melts and a weld is created upon re-solidification ofboth components. However, in some cases it is desired that the firstcomponent, which is transparent to laser light longer than 800 nm, alsobe inscribed with data. Even more desirable is the ability to inscribe atransparent, colored, opaque or dark colored first component suitablefor LTW with a light mark. Thus, there is a need for the ability togenerate a light colored mark on thermoplastic compositions.

It can also be desirable to be able to generate a range of contrastlevels from an easily readable (e.g., light colored) mark to asemi-covert, barely visible, inscription with as little increase to theprofile topography as possible, in order to eliminate the possibility ofthe layers lifting, separating, and/or cracking, for example when alaser inscription or mark is generated at the interface of two layers orat the interface of a thermoplastic layer and a coating. The change inthe profile topography via carbonization, to form a dark mark or,alternatively, a swelling from a foaming process, can give profiles muchlarger than 50 micrometers and even larger than 100 micrometers. Thegeneration of UV active or colored text, logos, barcodes or images,which are often incorporated into EID (“Electronic Identification”)cards passports, and pharmaceutical packaging requires the applicationof specialized inks and printing procedures. However, the specializedinks and printing procedures are costly and time consuming. Thus, a needexists to provide thermoplastic compositions with a customizable,machine-readable security function using a laser to generate microdotsthat exhibit either a different color under ultra-violet (UV) lightsource or are visibly of different color to the background.

SUMMARY

In one embodiment, an article for laser marking can comprising: athermoplastic composition comprising a thermoplastic polymer, an activecomponent comprising at least one of a polymeric unit and an additive,wherein the thermoplastic polymer has a visible transmission of greaterthan or equal to 80% according to ASTM D1003-00, Procedure A, using D65illumination, 10 degrees observer, and thickness of 1 mm; and a markproduced by chemical rearrangement of the active component generated bya laser of a first wavelength; wherein the mark exhibits at least oneof: (i) a change in optical properties in the region 400 nm to 700 nmwhen exposed to light having a wavelength less than or equal to 500 nm;and (ii) a change in optical properties in the region of 400 nm to 700nm when exposed to light having a wavelength greater than or equal tothe first wavelength.

A multilayered article for laser marking comprising: a first layerhaving a visible transmission of greater than or equal to 80% accordingto ASTM D1003-00, Procedure A, using D65 illumination, 10 degreesobserver, at a thickness of the first layer in the multilayer article; asecond layer having a visible transmission of greater than or equal to80% according to ASTM D1003-00, Procedure A, using D65 illumination, 10degrees observer, at a thickness of the second layer in the multilayerarticle, and wherein the second layer comprises an active component thatwill form a laser mark with an L* of less than or equal to 40 asmeasured according to CIELAB 1976 (specular included), when exposed to alaser light of a wavelength of greater than 800 nm; a third layerreflective to laser light having a wavelength greater than 800 nm,wherein the third layer has a visible transmission of greater than orequal to 80% according to ASTM D1003-00, Procedure A, using D65illumination, 10 degrees observer, at a thickness of the third layer inthe multilayer article; and optionally a substrate; wherein the articlecomprises a laser mark having an L* of less than or equal to 40 asmeasured according to CIELAB 1976 (specular included).

A multilayered article for laser marking comprising: a first layerhaving a visible transmission of greater than or equal to 80% accordingto ASTM D1003-00, Procedure A, using D65 illumination, 10 degreesobserver, at a thickness of the first layer in the multilayer article; asecond layer having a visible transmission of greater than or equal to80% according to ASTM D1003-00, Procedure A, using D65 illumination, 10degrees observer, at a thickness of the second layer in the multilayerarticle, and wherein the second layer comprises an active component thatwill form a laser mark with an L* of less than or equal to 40 asmeasured according to CIELAB 1976 (specular included), when exposed to alaser light of a wavelength of greater than 800 nm; and a non-whitesubstrate.

In another embodiment, a multilayered article, comprises: a first layerhaving a visible transmission of greater than or equal to 80% accordingto ASTM D1003-00, Procedure A, using D65 illumination, 10 degreesobserver, at a thickness of the first layer in the multilayer article;and a second layer, active to laser light having a wavelength less thanor equal to 500 nm, wherein the second layer is active via an activecomponent that will form a laser mark with an L* of less than or equalto 40 when exposed to a laser light of a wavelength of less than orequal to 500 nm; wherein the article comprises a laser mark having amark L* less than or equal to 40, as measured according to CIELAB 1976(specular included).

Further details and features of the present article and method are setforth below.

BRIEF DESCRIPTION OF THE DRAWINGS

The following is a brief description of the drawings wherein likeelements are numbered alike and which are presented for the purposes ofillustrating the exemplary embodiments disclosed herein and not for thepurposes of limiting the same.

FIG. 1 is a schematic view of the laser welding process disclosed hereinillustrating the laser marking options and positions.

FIG. 2 is a scanned image of Comparative Example 1 on a white backgroundand which was inscribed with a 1064 nanometer laser beam.

FIG. 3 is a scanned image of Comparative Example 2 on a white backgroundand which was inscribed with a 1064 nanometer laser beam.

FIG. 4 is a scanned image of Comparative Example 3 on a white backgroundand which was inscribed with a 1064 nanometer laser beam.

FIG. 5 is a picture of Sample 22 that was laser inscribed with a 355nanometer laser beam and placed on a black background.

FIG. 6 is a scanned image in transmission mode illustrating the laserinscriptions on Sample 22 including text and barcodes (left image) andan optical image obtained using a microscope of a magnified part of thelaser inscription viewed in transmission mode (right image).

FIG. 7 is a scanning electron microscopic image of the marked square inthe lower left hand corner of the matrix of Sample 22 as illustrated inFIG. 5.

FIG. 8 is an optical image in transmission mode illustrating laserinscribed dots.

FIG. 9 is a photographic image of Sample 35 showing a light mark on aRAL 9010-GL background, created using a laser beam having a wavelengthless than 500 nanometers and a dark mark on a RAL 9005-GL background,created using a laser beam having a wavelength greater than 500nanometers.

FIG. 10 is a photographic image of Sample 36 laser welded to Sample 40using a laser beam having a wavelength greater than 800 nanometers wherethe left image is the laser mark on the lower part (Sample 40), whilethe right image is the laser mark on the upper part (Sample 36).

FIG. 11 is a photographic image of a laser inscribed 2.5 mm thick sampleof sample No. 69 of Table 19 placed on a black background to illustratecolor and contrast of mark.

FIG. 12 is a photographic image of sample No. 80.

FIG. 13 is a photographic image of sample No. 80.

FIG. 14 is a photographic image of laser marked sample 70 on a whitebackground viewed under standard lighting (left) and black light(right).

FIG. 15 is a photographic image of Samples 91 and 93 against a whitebackground.

DETAILED DESCRIPTION

Disclosed herein is a process that can inscribe transparent, opaque,and/or colored thermoplastic compositions having low visiblereflectivity with microdots that can be arranged to form customizable,and, optionally, machine-readable light colored text, logos, barcodes,and images using a laser beam to generate microdots. As used herein, amicrodot is a single interaction site, which can be arranged to generatemarks, logos, text, etc. of different optical properties (e.g.,reflectivity) to the background wherein the mark can be clearly visible(e.g., identifiable by the human eye without magnification) tosemi-covert (e.g., barely visible to the human eye). Laser beam andlaser light are used interchangeably herein. It is to be understood thatby laser beam as used herein does not refer to only a narrow projectionof light, but also refers to and encompasses a broad array of light. Acolorant can be added to a natural, uncolored material (e.g., neatresin) without changing the reflectivity. As described herein, a processor method has been developed to generate a light colored mark ontransparent thermoplastic compositions, including compositionscomprising polymers such as polycarbonate, bisphenol-A polycarbonatebased copolymers, polyesters, polymethyl methacrylate (PMMA),polystyrene, polybutylene terephthalate, polyolefins, polyamides,polyvinylchloride, polylactic acid, and combinations comprising at leastone of the foregoing, at or below the surface of an article, using laserbeams having a wavelength less than or equal to 1000 nm. Some polymerscan produce such an effect but the method described herein can provide amethod to generate compositions that can enhance the process ofgenerating a laser mark or even make it possible to generate a lasermark in compositions where a laser light cannot typically generate amark. Table 1 provides an overview of laser types and the mechanisms bywhich they mark a thermoplastic substrate.

TABLE 1 Laser Information Laser Laser/Substrate Interaction WavelengthReaction CO₂ Engraving of metals/ 10,640 nm   Heat induced polymers IR(red) Carbonization and foaming of 1,064 nm   Heat induced polymersAblation of thin layers (lacquer or film) Green Carbonization andfoaming of 532 nm Heat induced polymers and Photo- Ablation of thinlayers chemistry (lacquer or film) Cutting of foils UV “Cold marking”355 nm Photochemistry without thermal interaction Excimer “Cold marking”170 nm to Photochemistry without thermal interaction 351 nm

An additive, e.g., an absorbing additive such as an ultravioletabsorbing additive and/or colorant can be added to a composition, e.g.,a transparent thermoplastic such as polycarbonate, bisphenol-A basedpolycarbonate copolymers, polyesters, PMMA, polystyrene, polybutyleneterephthalate, polyolefins, polyamide, polyvinylchloride, polylacticacid, and combinations comprising at least one of the foregoing Theadditive can allow for the use of laser beams with a wavelength lessthan or equal to 2,000 nm, specifically, less than or equal to 1000 nm,and even more specifically, less than or equal to 500 nm to interactwith the substrate and alter the reflectivity to produce a light coloredmark via a thermal mechanism.

The compositions and methods described herein can allow light coloredtext, logos, and/or other identifiers to be inscribed or marked on orclose to the surface of thermoplastic compositions (e.g., transparentthermoplastic compositions) at wavelengths of about 200 nm to 700 nm,specifically, 200 nm to 500 nm. For example, a white colored mark can beinscribed on a transparent material. As described herein, light coloredcan mean a white mark, where white can generally be described as white,off white, bright white ivory, snow, pearl, antique white, chalk, milkwhite, lily, smoke, seashell, old lace, cream, linen, ghost white,beige, cornsilk, alabaster, paper, whitewash, etc. The intensity andcolor of the mark can be modulated by varying laser parameters such aspower, frequency, speed, line spacing, and focus, which allows marks ofvarying degrees of legibility or clarity to be generated. The legibilityof the laser mark, whether on or close to the surface of the substrate,can be modulated from an easily readable light colored mark to asemi-covert, barely visible inscription, which may require specializedand sophisticated viewing devices to read and interpret the data. Theresulting watermark or ghost mark can be used as a semi-covert method ofidentification and/or traceability for material or productidentification. A watermark can generally be described as a recognizableimage that appears when viewed by transmitted light (or when viewed byreflected light, atop a dark background) at specific angles. Watermarkscan vary greatly in their visibility; while some are obvious on casualinspection, others require some study to observe.

Without wishing to be bound by theory, it is believed that the treatmentof the disclosed compositions with laser light having a wavelength lessthan or equal to 500 nm can produce a thermal interaction. In otherwords, the inscription can be a result of localized melting to generatean extremely small optically different, reflective or light scatteringdot or array of dots. This is illustrated in FIG. 7, which shows ascanning electron microscopic (SEM) image of the bottom left squareillustrated by reference number 30 in FIG. 5. The image in FIG. 7illustrates that a UV laser induced thermal process can occur (i.e.,melting at the surface). The composition and the laser process cancontrol the light scattering effect of the individual dots or array ofdots. Hence, the durability of the mark can therefore be as “tough” ordurable as the substrate itself (e.g., cannot be scratched off).

The surprising thermal interaction between the disclosed compositionswith laser light having a wavelength less than or equal to 500 nm canallow a laser light having a wavelength less than or equal to 500 nm tobe used to join or weld two different components (e.g., a firstcomponent and a substrate) comprised of thermoplastic compositions suchas polycarbonate, bisphenol-A based polycarbonate copolymers,polyesters, PMMA, polystyrene, polybutylene terephthalate, polyolefins,polyamides, polyvinylchloride, polylactic acid, and combinationscomprising at least one of the foregoing. The components have differentlevels of absorption, transparency, and interaction to the laser beamhaving a wavelength less than or equal to 500 nm, such that the laserbeam can pass through the first component without interaction and canthen be absorbed by the second component to generate heat at theinterface. The heat can then be conducted to the first layer, whichmelts, and a weld can be created upon resolidification of thecomponents.

Further herein disclosed are articles that can comprise a firstcomponent comprising a first composition, and a second component (e.g.,substrate) comprising a second composition where the first compositioncan comprise a polymer having little to no near infrared absorption atwavelengths greater than 800 nm to allow sufficient thermal build-up atthe interface between the two components, which can allow the firstcomponent to be welded to the second component with a laser beam (e.g.,laser light) having a wavelength longer than 800 nm. Such polymersinclude, but are not limited to non-scattering polymers such aspolycarbonate, bisphenol-A based polycarbonate copolymers, polyesters,PMMA, polystyrene, and polyamides, and non-absorbing scatteringcrystalline or semi-crystalline polymers such as polybutyleneterephthalate (PBT), polyethylene terephthalate (PET), polyolefins(e.g., high/low density polyethylene (H/LDPE), polypropylene (PP),etc.), and combinations comprising at least one of the foregoing. Havinglittle to no infrared absorption at wavelengths greater than 800 nm canallow the first component to be attached (e.g., laser welded) to thesubstrate comprising a second composition that absorbs light atwavelengths greater than 800 nm and can be joined to the first componentby a laser beam having light at wavelengths greater than 800 nm. Thefirst composition can be visibly transparent, colored, and/or opaque,using non-infrared absorbing colorants or additives and can be capableof being inscribed with laser light at wavelengths less than 800 nm,specifically, less than 500 nm. Such a feature can be beneficial inapplications where the first component is the viewed and authenticatedcomponent. Likewise, the substrate can be visibly transparent, colored,opaque, and/or un-pigmented (i.e., not colored).

The inscription (i.e., laser marking) can be located on the surface ofthe first component and/or the substrate. In processes such as two shotmolding, over-molding, or a laser welded set-up, the inscription can belocated within the first component (e.g., in the first shot) with nointeraction with the substrate material or other components housed bythe disclosed compositions. Not to be limited by theory, it is believedthat the inscriptions disclosed herein are a result of near surfacemodification, rather than a through surface modification as is the casewith carbonized marks or the result of foaming, which increases the voidvolume of the material. It is believed that the methods disclosed hereincan generate a mark (i.e., inscription) without increasing the voidvolume of the material.

The inscription can also occur at the interface of two components (e.g.,two layers), wherein the first component does not interact with thelaser beam and the second component interacts with the laser beam toalter the optical properties (e.g., reflectivity) of the secondcomponent at the point of interaction, where the laser beam has awavelength of less than or equal to 2,000 nm, specifically, less than orequal to 1,000 nm, and even more specifically, less than or equal to 500nm. In either case, the inscription can be durable (i.e., cannot bescratched off the surface). The appearance of the inscription can changewhen viewed from either side of the material. For example, with a neatresin (i.e., no colorant), with all other parameters the same, similarresults can be obtained from both sides of the article (i.e., front andback), meaning that the reflectivities are close to one another. The useof electromagnetic radiation to create a visibly perceivable laserinscribed contrast on a polymer material as described herein can rangefrom clearly visible from poorly visible and/or visible under onlyspecific lighting/viewing conditions (e.g., a watermark). The appearanceof the contrast area can be manipulated by controlling the change inmorphology of the polymeric material by changing the electromagneticradiation variables.

Various articles comprising the inscriptions are described herein. Thefollowing description of articles is merely illustrative of articlesthat can be produced and inscribed using the methods disclosed hereinand are not intended to limit the scope hereof. For example, the methodsdisclosed herein can be used to laser inscribe microdots exhibiting avariation in reflectivity compared to an unmarked substrate, at or belowthe surface of the substrate, with the microdots being arranged andmodulated in intensity using the laser parameters to generate logos,texts, barcodes, and/or images (e.g., photographic images) in thefollowing exemplified articles: glazing parts such as automotive panelsand lamp bezels in which the mark, including a watermark, can beintroduced on the surface of the part, pre- or post-coating and can alsobe placed over second shot areas to increase contrast; pharmaceutical orfood packaging marks, including watermarks; electronic housings orscreens in phones, computers, tablets, televisions, etc., where themark, including a watermark, is on the surface or at the interface oftwo components, for example, where the first component comprises PMMAand the second component comprises polycarbonate; mark, including awatermark, on eyewear lenses and frames; an article with an image,including a photographic image, which is visible in positive or negativedepending on whether the observer is viewing the image in transmissionor reflection; contact recognition or Braille inscriptions; and marks,including a watermark, on the surface or subsurface at the interface oftwo layers within cards or tickets such as business cards,identification (ID) cards, customer cards, etc. The mark can begenerated on the surface or at the interface of two layers (e.g., twocomponents) wherein the entire card is transparent or exists as a windowin an opaque card. Other possible layers in the ID card can include ametallic layer, a magnetic layer, a layer with angular metamerismproperties, and combinations comprising at least one of the foregoing.The layers can be assembled via various processes including, but notlimited to co-extrusion, co-lamination, etc.

More specifically, ID cards can, for example, comprise a core layer(e.g., reflective thermoplastic layer), and a transparent film layercomprising the compositions disclosed herein (e.g., either a materialhaving the capability of absorbing light at wavelengths less than orequal to 500 nm or a material comprising a light absorbing additivehaving the capability of absorbing light at wavelengths less than orequal to 500 nm). Optionally, a cap layer can be disposed on a side ofthe transparent film layer opposite the core layer, e.g., to protectagainst scratches, provide added chemical resistance, and/or lightresistance. Other layers having a thickness of less than or equal to 100micrometers can be formed first by an extrusion, a melt casting, orsolvent casting process, and optionally, stretched to reach the desiredthickness. The cap layers, and other, optional layer(s) can be added(e.g., in the form of a coating that can be cured by an energy sourcesuch as an ultra violet lamp).

FIG. 1 illustrates a schematic of the process used to laser weld twocomponents and form an article 10. In FIG. 1, laser exposure 14 (e.g., alaser beam) is directed through the first component 12 (e.g., atransparent polymer) to a second component 16 (e.g., a substrate that islaser absorbing), where laser exposure 14 is absorbed, resulting in theformation of heat at the interface 18 of the two layers. The heatinggenerates a local melt pool 20 between the layers resulting in a weld ofthe first thermoplastic component 12 to the second laser weldablecomponent 16. The laser exposure 14 generally follows a linear path ofoverlapping spot exposures to produce a welded seam 22. The secondcomponent 16 can additionally comprise an absorbing additive to enhanceabsorption of light from the laser beam.

Possible thermoplastic resins that may be employed include, but are notlimited to, oligomers, polymers, ionomers, dendrimers, copolymers suchas graft copolymers, block copolymers (e.g., star block copolymers,random copolymers, etc.) and combinations comprising at least one of theforegoing. Examples of such thermoplastic resins include, but are notlimited to, polycarbonates (e.g., blends of polycarbonate (such as,polycarbonate-polybutadiene blends, copolyester polycarbonates)),polystyrenes (e.g., copolymers of polycarbonate and styrene,polyphenylene ether-polystyrene blends), polyimides (e.g.,polyetherimides), acrylonitrile-styrene-butadiene (ABS),polyalkylmethacrylates (e.g., polymethylmethacrylates (PMMA)),polyesters (e.g., copolyesters, polythioesters), polyolefins (e.g.,polypropylenes (PP) and polyethylenes, high density polyethylenes(HDPE), low density polyethylenes (LDPE), linear low densitypolyethylenes (LLDPE)), polyamides (e.g., polyamideimides),polyarylates, polysulfones (e.g., polyarylsulfones, polysulfonamides),polyphenylene sulfides, polytetrafluoroethylenes, polyethers (e.g.,polyether ketones (PEK), polyether etherketones (PEEK),polyethersulfones (PES)), polyacrylics, polyacetals, polybenzoxazoles(e.g., polybenzothiazinophenothiazines, polybenzothiazoles),polyoxadiazoles, polypyrazinoquinoxalines, polypyromellitimides,polyquinoxalines, polybenzimidazoles, polyoxindoles, polyoxoisoindolines(e.g., polydioxoisoindolines), polytriazines, polypyridazines,polypiperazines, polypyridines, polypiperidines, polytriazoles,polypyrazoles, polypyrrolidines, polycarboranes, polyoxabicyclononanes,polydibenzofurans, polyphthalides, polyacetals, polyanhydrides,polyvinyls (e.g., polyvinyl ethers, polyvinyl thioethers, polyvinylalcohols, polyvinyl ketones, polyvinyl halides, polyvinyl nitriles,polyvinyl esters, polyvinylchlorides), polybutylene terephthalate (PBT),polysulfonates, polysulfides, polyureas, polyphosphazenes,polysilazzanes, polysiloxanes, fluoropolymers (e.g., polyvinyl fluoride(PVF), polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF),fluorinated ethylene-propylene (FEP), polyethylenetetrafluoroethylene(ETFE)) and combinations comprising at least one of the foregoing.

More particularly, the thermoplastic resin can include, but is notlimited to, polycarbonate resins (e.g., Lexan™ resins, commerciallyavailable from SABIC Innovative Plastics), polyphenyleneether-polystyrene resins (e.g., Noryl™ resins, commercially availablefrom SABIC Innovative Plastics), polyetherimide resins (e.g., Ultem™resins, commercially available from SABIC Innovative Plastics),polybutylene terephthalate and/or polyethylene terephthalate resins(e.g., Valox™ resins, commercially available from SABIC InnovativePlastics), polybutylene terephthalate-polycarbonate resins (e.g., Xenoy™resins, commercially available from SABIC Innovative Plastics),copolyestercarbonate resins (e.g. Lexan™ SLX resins, commerciallyavailable from SABIC Innovative Plastics), and combinations comprisingat least one of the foregoing resins. Even more particularly, thethermoplastic resins can include, but are not limited to, homopolymersand copolymers of a polycarbonate, a polyester, a polyacrylate, apolyamide, a polyetherimide, a polyphenylene ether, or a combinationcomprising at least one of the foregoing resins. The polycarbonate cancomprise copolymers of polycarbonate (e.g., polycarbonate-polysiloxane,such as polycarbonate-polysiloxane block copolymer), linearpolycarbonate, branched polycarbonate, end-capped polycarbonate (e.g.,nitrile end-capped polycarbonate), and combinations comprising at leastone of the foregoing, for example, a combination of branched and linearpolycarbonate.

As used herein, the term “polycarbonate” means compositions havingrepeating structural carbonate units of formula (1)

in which at least 60 percent of the total number of R¹ groups containaromatic moieties and the balance thereof are aliphatic, alicyclic, oraromatic. In an embodiment, each R¹ is a C₆₋₃₀ aromatic group, that is,contains at least one aromatic moiety. R¹ can be derived from adihydroxy compound of the formula HO—R¹—OH, in particular of formula (2)HO-A¹-Y¹-A²-OH  (2)wherein each of A¹ and A² is a monocyclic divalent aromatic group and Y¹is a single bond or a bridging group having one or more atoms thatseparate A¹ from A². In an exemplary embodiment, one atom separates A¹from A². Specifically, each R¹ can be derived from a dihydroxy aromaticcompound of formula (3)

wherein R^(a) and R^(b) each represent a halogen or C₁₋₁₂ alkyl groupand can be the same or different; and p and q are each independentlyintegers of 0 to 4. It will be understood that R^(a) is hydrogen when pis 0, and likewise R^(b) is hydrogen when q is 0. Also in formula (3),X^(a) represents a bridging group connecting the two hydroxy-substitutedaromatic groups, where the bridging group and the hydroxy substituent ofeach C₆ arylene group are disposed ortho, meta, or para (specificallypara) to each other on the C₆ arylene group. In an embodiment, thebridging group X^(a) is single bond, —O—, —S—, —S(O)—, —S(O)₂—, —C(O)—,or a C₁₋₁₈ organic group. The C₁₋₁₈ organic bridging group can be cyclicor acyclic, aromatic or non-aromatic, and can further compriseheteroatoms such as halogens, oxygen, nitrogen, sulfur, silicon, orphosphorous. The C₁₋₁₈ organic group can be disposed such that the C₆arylene groups connected thereto are each connected to a commonalkylidene carbon or to different carbons of the C₁₋₁₈ organic bridginggroup. In one embodiment, p and q are each 1, and R^(a) and R^(b) areeach a C₁₋₃ alkyl group, specifically methyl, disposed meta to thehydroxy group on each arylene group.

In an embodiment, X^(a) is a substituted or unsubstituted C₃₋₁₈cycloalkylidene, a C₁₋₂₅ alkylidene of formula —C(R^(c))(R^(d))— whereinR^(c) and R^(d) are each independently hydrogen, C₁₋₁₂ alkyl, C₁₋₁₂cycloalkyl, C₇₋₁₂ arylalkyl, C₁₋₁₂ heteroalkyl, or cyclic C₇₋₁₂heteroarylalkyl, or a group of the formula —C(═R^(e))— wherein R^(e) isa divalent C₁₋₁₂ hydrocarbon group. Exemplary groups of this typeinclude methylene, cyclohexylmethylene, ethylidene, neopentylidene, andisopropylidene, as well as 2-[2.2.1]-bicycloheptylidene,cyclohexylidene, cyclopentylidene, cyclododecylidene, andadamantylidene. A specific example wherein X^(a) is a substitutedcycloalkylidene is the cyclohexylidene-bridged, alkyl-substitutedbisphenol of formula (4)

wherein R^(a′) and R^(b′) are each independently C₁₋₁₂ alkyl, R^(g) isC₁₋₁₂ alkyl or halogen, r and s are each independently 1 to 4, and t is0 to 10. In a specific embodiment, at least one of each of R^(a′) andR^(b′) are disposed meta to the cyclohexylidene bridging group. Thesubstituents R^(a′), R^(b′), and R^(g) can, when comprising anappropriate number of carbon atoms, be straight chain, cyclic, bicyclic,branched, saturated, or unsaturated. In an embodiment, R^(a′) and R^(b′)are each independently C₁₋₄ alkyl, R^(g) is C₁₋₄ alkyl, r and s are each1, and t is 0 to 5. In another specific embodiment, R^(a′), R^(b′) andR^(g) are each methyl, r and s are each 1, and t is 0 or 3. Thecyclohexylidene-bridged bisphenol can be the reaction product of twomoles of o-cresol with one mole of cyclohexanone. In another exemplaryembodiment, the cyclohexylidene-bridged bisphenol is the reactionproduct of two moles of a cresol with one mole of a hydrogenatedisophorone (e.g., 1,1,3-trimethyl-3-cyclohexane-5-one). Suchcyclohexane-containing bisphenols, for example the reaction product oftwo moles of a phenol with one mole of a hydrogenated isophorone, areuseful for making polycarbonate polymers with high glass transitiontemperatures and high heat distortion temperatures.

In another embodiment, X^(a) is a C₁₋₁₈ alkylene group, a C₃₋₁₈cycloalkylene group, a fused C₆₋₁₈ cycloalkylene group, or a group ofthe formula —B¹—W—B²— wherein B¹ and B² are the same or different C₁₋₆alkylene group and W is a C₃₋₁₂ cycloalkylidene group or a C₆₋₁₆ arylenegroup.

X^(a) can also be a substituted C₃₋₁₈ cycloalkylidene of formula (5)

wherein R^(r), R^(p), R^(q), and R^(t) are independently hydrogen,halogen, oxygen, or C₁₋₁₂ organic groups; I is a direct bond, a carbon,or a divalent oxygen, sulfur, or —N(Z)— where Z is hydrogen, halogen,hydroxy, C₁₋₁₂ alkyl, C₁₋₁₂ alkoxy, or C₁₋₁₂ acyl; h is 0 to 2, j is 1or 2, i is an integer of 0 or 1, and k is an integer of 0 to 3, with theproviso that at least two of R^(r), R^(p), R^(q), and R^(t) takentogether are a fused cycloaliphatic, aromatic, or heteroaromatic ring.It will be understood that where the fused ring is aromatic, the ring asshown in formula (5) will have an unsaturated carbon-carbon linkagewhere the ring is fused. When k is one and i is 0, the ring as shown informula (5) contains 4 carbon atoms, when k is 2, the ring as shown informula (5) contains 5 carbon atoms, and when k is 3, the ring contains6 carbon atoms. In one embodiment, two adjacent groups (e.g., R^(q) andR^(t) taken together) form an aromatic group, and in another embodiment,R^(q) and R^(t) taken together form one aromatic group and R^(r) andR^(p) taken together form a second aromatic group. When R^(q) and R^(t)taken together form an aromatic group, R^(p) can be a double-bondedoxygen atom, i.e., a ketone.

Other useful aromatic dihydroxy compounds of the formula HO—R¹—OHinclude compounds of formula (6)

wherein each R^(h) is independently a halogen atom, a C₁₋₁₀ hydrocarbylsuch as a C₁₋₁₀ alkyl group, a halogen-substituted C₁₋₁₀ alkyl group, aC₆₋₁₀ aryl group, or a halogen-substituted C₆₋₁₀ aryl group, and n is 0to 4. The halogen is usually bromine.

Some illustrative examples of specific aromatic dihydroxy compoundsinclude the following: 4,4′-dihydroxybiphenyl, 1,6-dihydroxynaphthalene,2,6-dihydroxynaphthalene, bis(4-hydroxyphenyl)methane,bis(4-hydroxyphenyl)diphenylmethane,bis(4-hydroxyphenyl)-1-naphthylmethane, 1,2-bis(4-hydroxyphenyl)ethane,1,1-bis(4-hydroxyphenyl)-1-phenylethane,2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane,bis(4-hydroxyphenyl)phenylmethane,2,2-bis(4-hydroxy-3-bromophenyl)propane,1,1-bis(hydroxyphenyl)cyclopentane, 1,1-bis(4-hydroxyphenyl)cyclohexane,1,1-bis(4-hydroxyphenyl)isobutene,1,1-bis(4-hydroxyphenyl)cyclododecane,trans-2,3-bis(4-hydroxyphenyl)-2-butene,2,2-bis(4-hydroxyphenyl)adamantane, alpha,alpha′-bis(4-hydroxyphenyl)toluene, bis(4-hydroxyphenyl)acetonitrile,2,2-bis(3-methyl-4-hydroxyphenyl)propane,2,2-bis(3-ethyl-4-hydroxyphenyl)propane,2,2-bis(3-n-propyl-4-hydroxyphenyl)propane,2,2-bis(3-isopropyl-4-hydroxyphenyl)propane,2,2-bis(3-sec-butyl-4-hydroxyphenyl)propane,2,2-bis(3-t-butyl-4-hydroxyphenyl)propane,2,2-bis(3-cyclohexyl-4-hydroxyphenyl)propane,2,2-bis(3-allyl-4-hydroxyphenyl)propane,2,2-bis(3-methoxy-4-hydroxyphenyl)propane,2,2-bis(4-hydroxyphenyl)hexafluoropropane,1,1-dichloro-2,2-bis(4-hydroxyphenyl)ethylene,1,1-dibromo-2,2-bis(4-hydroxyphenyl)ethylene,1,1-dichloro-2,2-bis(5-phenoxy-4-hydroxyphenyl)ethylene,4,4′-dihydroxybenzophenone, 3,3-bis(4-hydroxyphenyl)-2-butanone,1,6-bis(4-hydroxyphenyl)-1,6-hexanedione, ethylene glycolbis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)ether,bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide,bis(4-hydroxyphenyl)sulfone, 9,9-bis(4-hydroxyphenyl)fluorine,2,7-dihydroxypyrene,6,6′-dihydroxy-3,3,3′,3′-tetramethylspiro(bis)indane (“spirobiindanebisphenol”), 3,3-bis(4-hydroxyphenyl)phthalimide,2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene,2,7-dihydroxyphenoxathin, 2,7-dihydroxy-9,10-dimethylphenazine,3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, and2,7-dihydroxycarbazole, resorcinol, substituted resorcinol compoundssuch as 5-methyl resorcinol, 5-ethyl resorcinol, 5-propyl resorcinol,5-butyl resorcinol, 5-t-butyl resorcinol, 5-phenyl resorcinol, 5-cumylresorcinol, 2,4,5,6-tetrafluoro resorcinol, 2,4,5,6-tetrabromoresorcinol, or the like; catechol; hydroquinone; substitutedhydroquinones such as 2-methyl hydroquinone, 2-ethyl hydroquinone,2-propyl hydroquinone, 2-butyl hydroquinone, 2-t-butyl hydroquinone,2-phenyl hydroquinone, 2-cumyl hydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3,5,6-tetra-t-butyl hydroquinone, 2,3,5,6-tetrafluorohydroquinone, 2,3,5,6-tetrabromo hydroquinone, or the like, orcombinations comprising at least one of the foregoing dihydroxycompounds.

A specific type of copolymer is a polyester carbonate, also known as apolyester-polycarbonate. Such copolymers further contain, in addition torecurring carbonate chain units of formula (1), repeating units offormula (A)

wherein J is a divalent group derived from a dihydroxy compound, and canbe, for example, a C₂₋₁₀ alkylene, a C₆₋₂₀ cycloalkylene, a C₆₋₂₀arylene, or a polyoxyalkylene in which the alkylene groups contain 2 to6 carbon atoms, specifically 2, 3, or 4 carbon atoms; and T is adivalent group derived from a dicarboxylic acid, and can be, forexample, a C₂₋₁₀ alkylene, a C₆₋₂₀ cycloalkylene, or a C₆₋₂₀ arylene.Copolyesters containing a combination of different T and/or J groups canbe used. The polyesters can be branched or linear.

In an embodiment, J is a C₂₋₃₀ alkylene group having a straight chain,branched chain, or cyclic (including polycyclic) structure. In anotherembodiment, J is derived from a dihydroxy compound of formula (2) above.In another embodiment, J is derived from a bisphenol of formula (3)above. In another embodiment, J is derived from an aromatic dihydroxycompound of formula (6) above.

Aromatic dicarboxylic acids that can be used to prepare the polyesterunits include isophthalic or terephthalic acid,1,2-di(p-carboxyphenyl)ethane, 4,4′-dicarboxydiphenyl ether,4,4′-bisbenzoic acid, or a combination comprising at least one of theforegoing acids. Acids containing fused rings can also be present, suchas in 1,4-, 1,5-, or 2,6-naphthalenedicarboxylic acids. Specificdicarboxylic acids include terephthalic acid, isophthalic acid,naphthalene dicarboxylic acid, cyclohexane dicarboxylic acid, or acombination comprising at least one of the foregoing acids. A specificdicarboxylic acid comprises a combination of isophthalic acid andterephthalic acid wherein the weight ratio of isophthalic acid toterephthalic acid is 91:9 to 2:98. In another specific embodiment, J isa C₂₋₆ alkylene and T is p-phenylene, m-phenylene, naphthalene, adivalent cycloaliphatic group, or a combination thereof. This class ofpolyester includes the poly(alkylene terephthalates).

The molar ratio of ester units to carbonate units in the copolymers canvary broadly, for example 1:99 to 99:1, specifically 10:90 to 90:10,more specifically 25:75 to 75:25, depending on the desired properties ofthe final composition.

In a specific embodiment, the polyester unit of apolyester-polycarbonate is derived from the reaction of a combination ofisophthalic and terephthalic diacids (or derivatives thereof) withresorcinol. In another specific embodiment, the polyester unit of apolyester-polycarbonate is derived from the reaction of a combination ofisophthalic acid and terephthalic acid with bisphenol A. In a specificembodiment, the polycarbonate units are derived from bisphenol A. Inanother specific embodiment, the polycarbonate units are derived fromresorcinol and bisphenol A in a molar ratio of resorcinol carbonateunits to bisphenol A carbonate units of 1:99 to 99:1.

Polycarbonates and polyester-polycarbonate can be manufactured byprocesses such as interfacial polymerization and melt polymerization.Although the reaction conditions for interfacial polymerization canvary, an exemplary process generally involves dissolving or dispersing adihydric phenol reactant in aqueous caustic soda or potash, adding theresulting mixture to a water-immiscible solvent medium, and contactingthe reactants with a carbonate precursor in the presence of a catalystsuch as, for example, a tertiary amine or a phase transfer catalyst,under controlled pH conditions, e.g., 8 to 10. The water immisciblesolvent can be, for example, methylene chloride, 1,2-dichloroethane,chlorobenzene, toluene, and the like.

Exemplary carbonate precursors include a carbonyl halide such ascarbonyl bromide or carbonyl chloride, or a haloformate such as abishaloformates of a dihydric phenol (e.g., the bischloroformates ofbisphenol A, hydroquinone, or the like) or a glycol (e.g., thebishaloformate of ethylene glycol, neopentyl glycol, polyethyleneglycol, or the like). Combinations comprising at least one of theforegoing types of carbonate precursors can also be used. In anembodiment, an interfacial polymerization reaction to form carbonatelinkages uses phosgene as a carbonate precursor, and is referred to as aphosgenation reaction. In the manufacture of polyester-polycarbonates byinterfacial polymerization, rather than using the dicarboxylic acid ordiol per se, the reactive derivatives of the acid or diol, such as thecorresponding acid halides, in particular the acid dichlorides and theacid dibromides can be used. Thus, for example instead of usingisophthalic acid, terephthalic acid, or a combination comprising atleast one of the foregoing acids, isophthaloyl dichloride, terephthaloyldichloride, or a combination comprising at least one of the foregoingdichlorides can be used.

Specific examples of bisphenol compounds of formula (3) include1,1-bis(4-hydroxyphenyl) methane, 1,1-bis(4-hydroxyphenyl) ethane,2,2-bis(4-hydroxyphenyl) propane (hereinafter “bisphenol A” or “BPA”),2,2-bis(4-hydroxyphenyl) butane, 2,2-bis(4-hydroxyphenyl) octane,1,1-bis(4-hydroxyphenyl) propane, 1,1-bis(4-hydroxyphenyl) n-butane,2,2-bis(4-hydroxy-2-methylphenyl) propane,1,1-bis(4-hydroxy-t-butylphenyl) propane, 3,3-bis(4-hydroxyphenyl)phthalimidine, 2-phenyl-3,3-bis(4-hydroxyphenyl) phthalimidine(p,p-PPPBP), and 1,1-bis(4-hydroxy-3-methylphenyl)cyclohexane (DMBPC).Combinations comprising at least one of the foregoing dihydroxycompounds can also be used. In one specific embodiment, thepolycarbonate is a linear homopolymer derived from bisphenol A, in whicheach of A¹ and A² is p-phenylene and Y¹ is isopropylidene in formula(3).

The homopolymer of DMBPC carbonate, which is represented by the xportion of formula (7) or its copolymer with BPA carbonate has anoverall chemical structure represented by formula (7).

DMBPC carbonate can be co-polymerized with BPA carbonate to form a DMBPCBPA co-polycarbonate. For example, DMBPC based polycarbonate as acopolymer or homopolymer (DMBPC) can comprise 10 to 100 mol % DMBPCcarbonate and 90 to 0 mol % BPA carbonate, specifically, 25 mol % DMBPCcarbonate and 75 mol % BPA carbonate, more specifically, 50 mol % DMBPCcarbonate and 50 mol % BPA carbonate.

The method of making any of the polycarbonates herein described is notparticularly limited. It may be produced by any known method ofproducing polycarbonate including the interfacial process using phosgeneand/or the melt process using a diaryl carbonate, such as diphenylcarbonate or bismethyl salicyl carbonate, as the carbonate source.

The polycarbonate can comprise a PPC polymer comprising a BPA carbonateblock and an aromatic ester block (e.g., isophthalate and terephthalate)as shown in formula (8).

In an embodiment, the PPC polymer can comprise 10 mol % to 50 mol % BPAcarbonate blocks and 50 mol % to 90 mol % aromatic ester blocks,specifically, 20 mol % BPA blocks and 80 mol % aromatic ester blocks,with an isophthalate to terephthalate ratio of 93:7.

A specific example of dihydroxy compounds of formula (2) can be thefollowing formula (9)

(also known as 3,3-bis(4-hydroxyphenyl)-2-phenylisoindolin-1-one(PPPBP)) also known as 2-phenyl-3,3-bis(4-hydroxyphenyl)phthalimidine.

The dihydroxy compounds of formula (2) can also be the following formula(10)

wherein R₃ and R₅ are each independently a halogen or a C₁₋₆ alkylgroup, R₄ is a C₁₋₆ alkyl, phenyl, or phenyl substituted with up to fivehalogens or C₁₋₆ alkyl groups, and c is 0 to 4. In a specificembodiment, R₄ is a C₁₋₆ alkyl or phenyl group. In still anotherembodiment, R₄ is a methyl or phenyl group. In another specificembodiment, each c is 0.

The polycarbonate can comprise a copolymer of p,p-PPPBP carbonate asdescribed with respect to formulas (9) and (10) and BPA carbonate, wherethe copolymer has the structure illustrated in formula (11).

The copolymer of p,p-PPPBP carbonate and BPA carbonate can comprise 25mol % to 75 mol % p,p-PPPBP carbonate and 75 mol % to 25 mol % BPAcarbonate, specifically, 35 mol % p,p-PPPBP carbonate and 65 mol % BPAcarbonate.

The composition further comprises a polysiloxane-polycarbonatecopolymer, also referred to as a poly(siloxane-carbonate). Thepolydiorganosiloxane (also referred to herein as “polysiloxane”) blocksof the copolymer comprise repeating diorganosiloxane units as in formula(10)

wherein each R is independently a C₁₋₁₃ monovalent organic group. Forexample, R can be a C₁-C₁₃ alkyl, C₁-C₁₃ alkoxy, C₂-C₁₃ alkenyl, C₂-C₁₃alkenyloxy, C₃-C₆ cycloalkyl, C₃-C₆ cycloalkoxy, C₆-C₁₄ aryl, C₆-C₁₀aryloxy, C₇-C₁₃ arylalkyl, C₇-C₁₃ aralkoxy, C₇-C₁₃ alkylaryl, or C₇-C₁₃alkylaryloxy. The foregoing groups can be fully or partially halogenatedwith fluorine, chlorine, bromine, or iodine, or a combination thereof.In an embodiment, where a transparent polysiloxane-polycarbonate isdesired, R is unsubstituted by halogen. Combinations of the foregoing Rgroups can be used in the same copolymer.

The value of E in formula (10) can vary widely depending on the type andrelative amount of each component in the thermoplastic composition, thedesired properties of the composition, and like considerations.Generally, E has an average value of 2 to 1,000, specifically 2 to 500,2 to 200, or 2 to 125, 5 to 80, or 10 to 70. In an embodiment, E has anaverage value of 10 to 80 or 10 to 40, and in still another embodiment,E has an average value of 40 to 80, or 40 to 70. Where E is of a lowervalue, e.g., less than 40, it can be desirable to use a relativelylarger amount of the polycarbonate-polysiloxane copolymer. Conversely,where E is of a higher value, e.g., greater than 40, a relatively loweramount of the polycarbonate-polysiloxane copolymer can be used.

A combination of a first and a second (or more)polycarbonate-polysiloxane copolymers can be used, wherein the averagevalue of E of the first copolymer is less than the average value of E ofthe second copolymer.

In an embodiment, the polydiorganosiloxane blocks are of formula (11)

wherein E is as defined above; each R can be the same or different, andis as defined above; and Ar can be the same or different, and is asubstituted or unsubstituted C₆-C₃₀ arylene, wherein the bonds aredirectly connected to an aromatic moiety. Ar groups in formula (11) canbe derived from a C₆-C₃₀ dihydroxyarylene compound, for example adihydroxyarylene compound of formula (3) or (6) above. dihydroxyarylenecompounds are 1,1-bis(4-hydroxyphenyl) methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl) propane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl) octane, 1,1-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl) n-butane,2,2-bis(4-hydroxy-1-methylphenyl) propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl sulfide), and1,1-bis(4-hydroxy-t-butylphenyl) propane. Combinations comprising atleast one of the foregoing dihydroxy compounds can also be used.

In another embodiment, polydiorganosiloxane blocks are of formula (13)

wherein R and E are as described above, and each R⁵ is independently adivalent C₁-C₃₀ organic group, and wherein the polymerized polysiloxaneunit is the reaction residue of its corresponding dihydroxy compound. Ina specific embodiment, the polydiorganosiloxane blocks are of formula(14):

wherein R and E are as defined above. R⁶ in formula (14) is a divalentC₂-C₈ aliphatic. Each M in formula (14) can be the same or different,and can be a halogen, cyano, nitro, C₁-C₈ alkylthio, C₁-C₈ alkyl, C₁-C₈alkoxy, C₂-C₈ alkenyl, C₂-C₈ alkenyloxy, C₃-C₈ cycloalkyl, C₃-C₈cycloalkoxy, C₆-C₁₀ aryl, C₆-C₁₀ aryloxy, C₇-C₁₂ aralkyl, C₇-C₁₂aralkoxy, C₇-C₁₂ alkylaryl, or C₇-C₁₂ alkylaryloxy, wherein each n isindependently 0, 1, 2, 3, or 4. In an embodiment, M is bromo or chloro,an alkyl such as methyl, ethyl, or propyl, an alkoxy such as methoxy,ethoxy, or propoxy, or an aryl such as phenyl, chlorophenyl, or tolyl;R⁶ is a dimethylene, trimethylene or tetramethylene; and R is a C₁₋₈alkyl, haloalkyl such as trifluoropropyl, cyanoalkyl, or aryl such asphenyl, chlorophenyl or tolyl. In another embodiment, R is methyl, or acombination of methyl and trifluoropropyl, or a combination of methyland phenyl. In still another embodiment, R is methyl, M is methoxy, n isone, R⁶ is a divalent C₁-C₃ aliphatic group. Specificpolydiorganosiloxane blocks are of the formula

or a combination comprising at least one of the foregoing, wherein E hasan average value of 2 to 200, 2 to 125, 5 to 125, 5 to 100, 5 to 50, 20to 80, or 5 to 20.

Transparent polysiloxane-polycarbonate copolymers comprise carbonateunits (1) derived from bisphenol A, and repeating siloxane units (14a),(14b), (14c), or a combination comprising at least one of the foregoing(specifically of formula 14a), wherein E has an average value of 4 to50, 4 to 15, specifically 5 to 15, more specifically 6 to 15, and stillmore specifically 7 to 10. The transparent copolymers can bemanufactured using one or both of the tube reactor processes describedin U.S. Patent Application No. 2004/0039145A1 or the process describedin U.S. Pat. No. 6,723,864 may be used to synthesize thepoly(siloxane-carbonate) copolymers.

Blocks of formula (14) can be derived from the corresponding dihydroxypolydiorganosiloxane (15)

wherein R, E, M, R⁶, and n are as described above. Such dihydroxypolysiloxanes can be made by effecting a platinum-catalyzed additionbetween a siloxane hydride of formula (16)

wherein R and E are as previously defined, and an aliphaticallyunsaturated monohydric phenol. aliphatically unsaturated monohydricphenols include eugenol, 2-alkylphenol, 4-allyl-2-methylphenol,4-allyl-2-phenylphenol, 4-allyl-2-bromophenol, 4-allyl-2-t-butoxyphenol,4-phenyl-2-phenylphenol, 2-methyl-4-propylphenol,2-allyl-4,6-dimethylphenol, 2-allyl-4-bromo-6-methylphenol,2-allyl-6-methoxy-4-methylphenol and 2-allyl-4,6-dimethylphenol.Combinations comprising at least one of the foregoing can also be used.The polysiloxane-polycarbonate copolymers can then be manufactured, forexample, by the methods described in U.S. Pat. No. 6,072,011 to Hoover.

The polyorganosiloxane-polycarbonate can comprise 50 to 99 weightpercent of carbonate units and 1 to 50 weight percent siloxane units.Within this range, the polyorganosiloxane-polycarbonate copolymer cancomprise 70 to 98 weight percent, more specifically 75 to 97 weightpercent of carbonate units and 2 to 30 weight percent, more specifically3 to 25 weight percent siloxane units.

Polyorganosiloxane-polycarbonates can have a weight average molecularweight of 2,000 to 100,000 Daltons, specifically 5,000 to 50,000 Daltonsas measured by gel permeation chromatography using a crosslinkedstyrene-divinyl benzene column, at a sample concentration of 1 milligramper milliliter, and as calibrated with polycarbonate standards.

The polyorganosiloxane-polycarbonate can have a melt volume flow rate,measured at 300° C./1.2 kg, of 1 to 50 cubic centimeters per 10 minutes(cc/10 min), specifically 2 to 30 cc/10 min. Mixtures ofpolyorganosiloxane-polycarbonates of different flow properties can beused to achieve the overall desired flow property.

The compositions can include various additives ordinarily incorporatedinto polymer compositions of this type, with the proviso that theadditive(s) are selected so as to not significantly adversely affect thedesired properties of the composition. Such additives can be mixed at asuitable time during the mixing of the composition. Exemplary additivesinclude impact modifiers, fillers, reinforcing agents, antioxidants,heat stabilizers, light stabilizers, ultraviolet (UV) light stabilizers,plasticizers, lubricants, mold release agents, antistatic agents,colorants (such as carbon black and organic dyes), surface effectadditives, radiation stabilizers (e.g., infrared absorbing), flameretardants, and anti-drip agents. A combination of additives can beused, for example a combination of a heat stabilizer, mold releaseagent, and ultraviolet light stabilizer. In general, the additives areused in the amounts generally known to be effective. The total amount ofadditives (other than any impact modifier, filler, or reinforcingagents) is generally 0.001 wt. % to 5 wt. %, based on the total weightof the composition.

Absorbing additives such as light stabilizers and/or ultraviolet light(UV) absorbing stabilizers can also be used. Exemplary light stabilizeradditives include benzotriazoles such as2-(2-hydroxy-5-methylphenyl)benzotriazole,2-(2-hydroxy-5-tert-octylphenyl)-benzotriazole and 2-hydroxy-4-n-octoxybenzophenone, or combinations comprising at least one of the foregoinglight stabilizers. Light stabilizers are used in amounts of 0.001 to 5parts by weight, based on 100 parts by weight of the total composition,excluding any filler.

Exemplary UV absorbing additives include hydroxybenzophenones;hydroxybenzotriazoles; hydroxybenzotriazines; cyanoacrylates;oxanilides; benzoxazinones benzylidene malonates; hindered amine lightstabilizers; nano-scale inorganics such as nickel quenchers, metaloxides, mixed metal oxides, metal borides; and combinations comprisingat least one of the foregoing;2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol (CYASORB™5411); 2-hydroxy-4-n-octyloxybenzophenone (CYASORB™ 531);2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-(octyloxy)-phenol(CYASORB™ 1164); 2,2′-(1,4-phenylene)bis(4H-3,1-benzoxazin-4-one)(CYASORB™ UV-3638);1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane(UVINUL™ 3030); 2,2′-(1,4-phenylene) bis(4H-3,1-benzoxazin-4-one);1,3-bis[(2-cyano-3,3-diphenylacryloyl)oxy]-2,2-bis[[(2-cyano-3,3-diphenylacryloyl)oxy]methyl]propane;nano-size inorganic materials such as titanium oxide, cerium oxide, andzinc oxide, all with particle size less than or equal to 100 nanometers,or combinations comprising at least one of the foregoing UV absorbers.UV absorbers are used in amounts of 0.001 to 5 parts by weight, based on100 parts by weight of the total composition, excluding any filler.Inorganic additives such as lanthanum hexaboride (LaB₆) or Cesiumtungsten oxide (CTO) can also be used to enhance the interaction ofcompositions with laser light and improve mark contrasts.

Colorants such as pigment and/or dye additives can also be present aloneor in combination with UV absorbing stabilizers having little residualvisible coloration in order to modulate the substrate color as well asthe color and contrast of the laser inscribed text, logos, barcodes,images, etc. by directly contributing to the change of reflectivity.Useful pigments can include, organic pigments such as azos, di-azos,quinacridones, perylenes, naphthalene tetracarboxylic acids,flavanthrones, isoindolinones, tetrachloroisoindolinones,anthraquinones, enthrones, dioxazines, phthalocyanines, and azo lakes;Pigment Red 101, Pigment Red 122, Pigment Red 149, Pigment Red 177,Pigment Red 179, Pigment Red 202, Pigment Violet 29, Pigment Blue 15,Pigment Blue 60, Pigment Green 7, Pigment Yellow 119, Pigment Yellow147, Pigment Yellow 150, and Pigment Brown 24; or combinationscomprising at least one of the foregoing pigments.

Exemplary dyes are generally organic materials and include coumarin dyessuch as coumarin 460 (blue), coumarin 6 (green), nile red or the like;lanthanide complexes; hydrocarbon and substituted hydrocarbon dyes;polycyclic aromatic hydrocarbon dyes; scintillation dyes such as oxazoleor oxadiazole dyes; aryl- or heteroaryl-substituted poly (C₂₋₈) olefindyes; carbocyanine dyes; indanthrone dyes; phthalocyanine dyes; oxazinedyes; carbostyryl dyes; napthalenetetracarboxylic acid dyes; porphyrindyes; bis(styryl)biphenyl dyes; acridine dyes; anthraquinone dyes;cyanine dyes; methine dyes; arylmethane dyes; azo dyes; indigoid dyes,thioindigoid dyes, diazonium dyes; nitro dyes; quinone imine dyes;aminoketone dyes; tetrazolium dyes; thiazole dyes; perylene dyes,perinone dyes; bis-benzoxazolylthiophene (BBOT); triarylmethane dyes;xanthene dyes; thioxanthene dyes; naphthalimide dyes; lactone dyes;fluorophores such as anti-stokes shift dyes which absorb in the nearinfrared wavelength and emit in the visible wavelength, or the like;luminescent dyes such as 7-amino-4-methylcoumarin;3-(2′-benzothiazolyl)-7-diethylaminocoumarin;2-(4-biphenylyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole;2,5-bis-(4-biphenylyl)-oxazole; 2,2′-dimethyl-p-quaterphenyl;2,2-dimethyl-p-terphenyl; 3,5,3″″,5″″-tetra-t-butyl-p-quinquephenyl;2,5-diphenylfuran; 2,5-diphenyloxazole; 4,4′-diphenylstilbene;4-dicyanomethylene-2-methyl-6-(p-dimethylaminostyryl)-4H-pyran;1,1′-diethyl-2,2′-carbocyanine iodide;3,3′-diethyl-4,4′,5,5′-dibenzothiatricarbocyanine iodide;7-dimethylamino-1-methyl-4-methoxy-8-azaquinolone-2;7-dimethylamino-4-methylquinolone-2;2-(4-(4-dimethylaminophenyl)-1,3-butadienyl)-3-ethylbenzothiazoliumperchlorate; 3-diethylamino-7-diethyliminophenoxazonium perchlorate;2-(1-naphthyl)-5-phenyloxazole; 2,2′-p-phenylen-bis(5-phenyloxazole);rhodamine 700; rhodamine 800; pyrene, chrysene, rubrene, coronene, orthe like; or combinations comprising at least one of the foregoing dyes.It is to be understood that any of the above described additives, UVabsorbers, colorants, etc. can be used with any of the materialsdescribed herein and is not limited to polycarbonate.

Further described herein is a process to achieve customizable, UV laserinscribed microdots that fluoresce under UV light and/or can be visiblycolored. In other words, the laser inscribed dots (e.g., that can beassembled into, for example, text, logos, barcodes, images, and soforth) fluoresce when illuminated with UV light. Optionally, these dotscan be different in color from the background. The compositions andprocesses allow the laser to inscribe data in various degrees oflegibility including a covert or at least semi-covert format (e.g.,barely visible to the unaided eye having normal vision). The UV laserinscribed microdots can be formed on a transparent thermoplastic (e.g.,Tvis>80%) composition comprising an additive or polymeric unitincorporating units based on Formula 1, disclosed above. Without beingbound by any particular theory, it is believed that the degree oflegibility can be achieved by causing a photo-chemical rearrangement ofan additive or polymer (backbone, side-chain or end-cap) within thecomposition wherein the visibility of the laser treated area becomesmore pronounced when viewed under UV light. The chemical rearrangementcan result in a change in the absorption of visible light that resultsin a color change. In the alternative, the chemical rearrangement canresult in a change in the reflectivity of visible light. The lasertreated area can additionally exhibit very subtle physical differences,which accounts for the visible differentiation of the laser treated areato the untreated parts. Thus, the use of UV active printing inks andprinting processes can be avoided. In addition, due to the nature of theUV active and/or colored laser inscribed microdots, formed as the resultof chemical re-arrangement, a thermoplastic substrate comprising thedots can advantageously be laminated (e.g., heat treated) withoutdiminishing or losing the fluorescence or colored laser inscribed image.In contrast, white marks generated by the heat of a UV laser, formed asa result of physical change, can be damaged or destroyed through theheat associated with a lamination process.

The laser treated microdot can have a different refractive index thanthe untreated area due to the photo-chemical rearrangement of anadditive or polymer (backbone, side-chain or end-cap) within thecomposition

Laser inscribed microdots at or below the surface of thermoplasticcompositions or substrates can be generated using lasers having awavelength shorter than 1000 nm, specifically at wavelengths shorterthan 800 nm, and more specifically shorter than 500 nm. The laserinscribed microdots can individually have dimensions of less than 200micrometers. Specifically, the laser inscribed microdots can havedimensions of less than 100 micrometers. More specifically, the laserinscribed microdots can have dimensions less than 50 micrometers. Thethermoplastic compositions include those set forth above and can alsocomprise an absorbing additive or colorant, in particular an ultravioletabsorbing additive or colorant, into or onto a transparentthermoplastic, such as polycarbonate (e.g., with moieties of aryl esterand/or diaryl carbonate) and/or BPA based co-polymer.

The visibility or legibility of the microdot arrangements under visiblelight can be tuned from clearly legible to semi-covert by modulating thelevel of interaction and hence the degree of scattering by the physicalsize/shape of the resulting microdot. The laser inscribed microdots arevisible under UV illumination (i.e., UV active) and, surprisingly, itwas found that the intensity of the UV response of the laser-inscribedmicrodots could be modulated by changing the laser parameters such aspower, frequency, speed, line spacing, and focus. For example, intensedots can be obtained using a laser with a track width of 0.03 mm, powerat 95%, velocity of 834 mm/s, pulse frequency of 27000 Hz, and Z-offsetof 8 and 12 mm, and having hatch settings using lines with a linesspacing of 0.03 mm, 0 mm margin spacing, 90 degree hatching angle, and 1hatching.

The UV active laser inscribed microdots can be visibly colored (i.e.,the localized, laser induced chemical change alters the interaction ofthe laser treated area to visible light compared to the untreated area)and can be assembled into legible text, logos, and other identifiers tobe inscribed or marked on or close to the surface of transparentthermoplastic compositions. The intensity and color of the visible markcan be modulated by varying the laser parameters such as power,frequency, speed, line spacing, focus and this allows marks of varyingdegrees of visible light viewed legibility or clarity to be generated.The visible light legibility of the laser inscribed microdots can betuned from an easily readable mark to a semi-covert, barely visibleinscription, which may require specialized and sophisticated viewingdevices to read and interpret the data or image.

The transparent thermoplastic can also comprise an additive or colorant,which is not normally active under UV light, but can become active whentreated with a laser having a wavelength shorter than 1000 nm.Specifically, a laser having a wavelength shorter than 800 nm, and morespecifically shorter than 500 nm. Hence, polymer compositions can bemodified with low molecular additives that undergo photo-chemicalrearrangements to produce areas which interact with light differently(either visible light or non-visible light, e.g., UV activefluorescence) than the un-treated background. For example, the use oflaser light of the described wavelength to generate microdots of a orthohydroxy-aryl carbonyl derivate, which when arranged into text, logos,barcodes or images exhibit a UV active color. The non-inscribed areasremain UV inactive. The concept includes, but is not limited to, laserinduced de-protection to generation a UV active fluorophore, such as ahydroxyl flavone.

The thermoplastic composition can comprise a photoactive additive orcolorant, which in certain media may be regarded as photochromic.Examples of additives can include members of the spiropyran,spirooxazine, fulgide, diarylethene, spirodihydroindolizine,azo-compounds, and Schiff base, benzo- and naphthopyrans families, andcombinations comprising at least one of the foregoing. Photochromism, asused herein, can be defined as a reversible transformation of a chemicalspecies (A and B), induced in one or both directions by electromagneticradiation as shown below:

The two states A and B have distinguishable light absorptions indifferent regions of the spectrum. Reversibility is the main criterionfor photochromism, as irreversible color change induced by light belongsto normal photochemical rearrangement category and cannot be regarded asphotochromism. Photochromic compounds require an environment in whichthey can reversibly transform. Without being bound by any particulartheory, in solid polymer matrices, the rate at which photochromicprocess of activation and fading is believed to be dependent on the freevolume in the polymer matrix. The free volume of the polymer matrix isrelated to the flexibility of the polymer chain segments surrounding thephotochromic compound. For example, the performance of photochromiccompounds in polycarbonate (PC) is poor because PC doesn't havesufficient internal free volume for them to function properly, i.e., toachieve an acceptable activated intensity and acceptable rate ofactivation and fade. As shown in FIG. 7, an SEM image of UV inscribedmicrodots indicates that the interaction has a thermal element. Thethermoplastic composition and process described herein allowsphotochromism to take place. In other words, the efficiency of theconversion to the B form described above can be increased as aconsequence of the increase in matrix free volume during the lasertreatment, i.e., the change of phase from solid to molten and theresulting increase in matrix flexibility. The color change can bepermanent, or the photo or thermal reversion to the form A can bedramatically slowed.

Further described herein a method and article that enables theproduction of consistent dark marks on any substrate regardless of colorand opacity. As used herein, a dark mark has an L* value of less than orequal to 40 (specular included), and specifically less than or equal to35 when measured on a white background. More specifically, a dark markcan have an L* less than or equal to 25 (specular excluded) and lessthan 20 when measured on a white background. Unless specifically statedotherwise, L* is determined according to ASTM E308-08 and CIELAB 1976.Previously, when a mark was formed on colored substrates, the color ofthe mark between different substrates was different. Consistency was notobtained. It has been discovered that by decoupling the mark from thesubstrate, any substrate can be used (e.g., any color and anytransparency). Hence, the substrate is not limited to a highlyreflective, white composition to obtain a consistent dark mark (ondifferent substrate samples).

When the mark was decoupled from the substrate, e.g., placed in a layerover the substrate, inconsistent dark marks were still formed.Surprisingly, a consistent dark mark was formed when the mark wasdecoupled from the substrate and located in a layer between atransparent layer (i.e., transmission less than or equal to 85% of thewavelength of laser light used to form the mark) and the substrate.

Hence, the multilayer article comprises a transparent layer disposed ona substrate, with a weak absorbing layer therebetween layer(s)restricting the interaction and the laser to that layer an assembly oftransparent layers comprising one or more sections that restricts orcontains the strong interaction required to generate a dark laser markto either the surface of, or within a particular layer or series oflayers. Thus, it is possible to decouple the strongest interaction ofthe laser from other layers, sections or substrates to enable aconsistent dark to gray-scale contrast regardless of the substrate coloror composition.

The articles can comprise a multilayer construct, wherein each layer canbe formed of 25 to 500 micrometers thick films or sections that aretransparent to visible light (e.g. Tvis of at least 80% measured by ASTMD103 Procedure A). Specifically, each layer can be 25 to 300 micrometersthick films or sections. More specifically, each layer can be 25 to 200micrometers thick films or sections. The articles can be comprised of atleast two layers, for achieving a dark laser mark. The sections areconstructed so as to contain or restrict the interaction of the laser toeither the surface of, or more specifically within, the transparentfilms or sections that are transparent to visible light. Each sectioncan be defined by the role or function it has with the laser light. Theprocess enables excellent dark to gray-scale contrast levels for logos,text, and images to be inscribed on or within the films or sections thatare transparent to visible light regardless of the substrate color orcomposition.

Transparent thermoplastic compositions can include compositionscomprising polymers such as polycarbonate, bisphenol-A polycarbonatebased copolymers, polyesters, polymethyl methacrylate (PMMA),polystyrene, polybutylene terephthalate, polyolefins, polyamides,polyvinylchloride, polylactic acid, and combinations thereof.

When the laser wavelength used to generate the dark mark has awavelength greater than 900 nm, e.g., 1064 nm, the construct of films orsections that is transparent to visible light comprises a transparentnear infrared (NIR) reflecting section (or multilayer) below a NIRabsorbing layer. The NIR absorbing layer can comprise laser absorbingadditives such as carbon black, lanthanum hexaboride, and/or cesiumtungsten oxide. An additional section that is transparent to visiblelight and is additionally NIR transparent can be adjoined to the NIRabsorbing layer. The article can contain a section or film that ispredominantly NIR transparent adjacent to or on top of the weak NIRabsorbing film or section.

The arrangement of films or sections that are transparent to visiblelight can be adjoined (for example via co-extrusion, lamination, or inmold decoration processes) to a substrate wherein the NIR reflectingsection (or multilayer) is adjacent to the substrate allowing aconsistent dark laser mark to be achieved regardless of the substratecomposition or color. In addition, the substrate can be opaque ortransparent and have a range of visible colors.

When the laser wavelength used to generate the dark mark is shorter than900 nm, specifically less than 500 nm, and more specifically less than400 nm, the layers that are transparent to visible light comprises aweak ultra violet absorbing (UVA) section. The weak UVA section can belocated below a section or film that is transparent in to ultravioletlight (UV). As used herein, weak UVA means a material that includes lessthan 200 ppm (parts per million) of an UV absorbent additive. Morespecifically, weak UVA can comprise less than 100 ppm of a UV absorbentadditive. Even more specifically, weak UVA can comprise less than 50 ppmof a UV absorbent additive. The UVA absorbent additive can comprise anUV absorbing polymer, resin, or additives such as carbon black,benzotriazoles such as 2-(2-hydroxy-5-methylphenyl)benzotriazole,2-(2-hydroxy-5-tert-octylphenyl)-benzotriazole and 2-hydroxy-4-n-octoxybenzophenone, nano-scale inorganic additives such as lanthanumhexaboride, cesium tungsten oxide, and combinations thereof. It wasfound that a darker mark could be applied when one or more UVtransparent layers are located above the UVA layer. As used herein, a UVtransparent layer is a layer that does not interact with a laser havinga wavelength of less than or equal to 500 nm. In other words, no mark isformed when the layer is exposed to a laser having a wavelength of lessthan or equal to 500 nm.

An additional strong UVA layer can be adjoined to the weak UVA section.As used herein, strong UVA means UV transmission less than 20%, and morespecifically less than 10% and even more preferably less than 10%. Theuse of a strong UVA layer allows for black and white images to beproduced on a transparent series of films. A white mark is applied tothe lower strong UVA section with a laser having a wavelength shorterthan 600 nm (specifically less than 500 nm and more specifically lessthan 400 nm). A dark mark is produced in the weak UVA layer byirradiating the sections via the UV transparent section.

An article can be an arrangement of films or sections that aretransparent to visible light and comprise at least a bilayer of weak andstrong UVA that are adjoined (e.g., via co-extrusion, lamination or inmold decoration processes). The substrate can be opaque or transparent.The strong UVA section can be adjacent to the substrate, which allows aconsistent dark laser mark to be achieved regardless of the substratecomposition or color. The composition can contain a section or film thatis predominantly UV transparent adjacent to or on top of the weak UVAsection.

The following examples are merely illustrative of the disclosed hereinand are not intended to limit the scope hereof.

EXAMPLES

Various compositions were tested to determine their interaction withlaser light and their ability to be inscribed. Thermoplastic testspecimens were prepared by melt extrusion on a Werner & Pfleiderer 25 mmtwin screw extruder, using a nominal melt temperature of 290° C. to 310°C., pressure of 25 inches (635 mm) of mercury vacuum and 450 revolutionsper minute (rpm). The extrudate was pelletized and dried at 110° C. for3 hours. Test specimens were produced (60 mm×60 mm×2 mm) from the driedpellets and were injection molded at nominal temperatures of 290° C. to320° C.

The color data was acquired on an X-rite I-7 spectrophotometer in therange 360 nm to 750 nm. The transmission data was acquired using a 25 mmaperture, while the reflection data was acquired in specular excludedmode using a 10 mm aperture with a RAL 9005-GL card placed behind thepart. RAL is a color standard used in Europe. The transmission andreflection data was measured using parts having a thickness of 1 mmaccording to ASTM D1003-00 using D65 illumination and 10 degreesobserver. The color from the laser inscribed areas was evaluated on a 15mm×15 mm square using the 10 mm aperture with a RAL 9005-GL card placedbehind the laser marked square. The visible transmission (i.e., Tvis)measurements were acquired on a HAZE-GUARD plus from BYK-Gardnerinstruments.

A Trumark 6330 laser (355 nm), which has a power output of 2 Watts (W),and a Trumark 6130 laser (1064 nm) were used to inscribe the test pieceswith a processing matrix consisting of a range of laser conditions suchas frequency of 20 to 40 kiloHertz (kHz), speed of 600 to 1800millimeters per second (mm/sec), and a fill factor of 0.03 to 0.45 mm,i.e., the spacing between adjacent lines of laser dots. The powersetting was 95% unless otherwise stated. Scanning electron microscopy(SEM) was used to acquire SEM micrographs using a FEI XL 30 microscope,operated at a voltage of 15 kiloVolts (kV). Samples were coated withgold (Au) and/or palladium (Pd) prior to the SEM investigation. Opticalimages were obtained using an Olympus BX60F microscope, in reflectionand transmission mode. The laser marked plaques were scanned using anEpson Perfection V750-Pro. The images were acquired with a 600 dot perinch (dpi) setting. The laser marked plaques were placed on a RAL9005-GL card and a RAL 9010-GL card was placed beside it for referencingon a scale of 0 to 255. The acquired images were evaluated using ImageJ1.44 software to measure the contrast on the front and the back of thesample (see e.g., Table 8).

Profilometry measurements were obtained using a Veeco Dektak 6M StylusProfiler using the following experimental conditions: scan length: 2700μm, resolution 0.265 μm/s, stylus force 3 mg. Calibration was performedusing a standard of known dimensions: nominal 10 KA (1 μm), measuringreport (SI).

For welding, high gloss surface test pieces were placed together withthe corresponding high gloss surface part, where the top samples werelaser transparent at wavelengths of greater than 800 nm and laserabsorbing at wavelengths less than 500 nm and the lower samples werelaser absorbing at wavelengths greater than 800 nm. The overlapped areawas then irradiated with a diode laser (960 nm) with a beam diameter of2 mm.

The materials used for the compositions are listed in Table 2. Sampleswere made using various combinations of the materials listed in Table 2.The samples were made as described above. The samples were then lasermarked with a UV laser (e.g., having a laser beam with a wavelength of355 nm) and a near infrared laser (NIR) (e.g., having a laser beam witha wavelength of 1064 nm) to determine the ability of the samples to bemarked. As described and used herein, UV light refers to light having awavelength of 10 nm to 400 nm, while near-infrared light refers to lighthaving a wavelength of 700 nm to 5,000 nm. Unless otherwise stated, thesamples had a thickness of 1 mm.

TABLE 2 Material Description Component Description Source PC1Bisphenol-A based polycarbonate resin Lexan ™ resin, SABIC (M_(w) =30,000 g/mol, PS standards) Innovative Plastics PC2 Bisphenol-A basedpolycarbonate resin Lexan ™ resin, SABIC (M_(w) = 22,000 g/mol, PSstandards) Innovative Plastics PC3 Poly(20 wt. % isophthalate- SABICInnovative terephthalate-resorcinol ester)-co-(80 Plastics wt. %bisphenol-A carbonate) copolymer (M_(w) = 60,000 g/mol, PS standards)PC4 Poly(90 wt. % isophthalate- SABIC Innovativeterephthalate-resorcinol)-co-(10 wt. % Plastics bisphenol-A carbonate)copolymer (M_(w) = 40,000 g/mol, PS standards) PC5 PC/PDMS copol (20%siloxane) SABIC Innovative Plastics PC6 DMBPC-BPA (50:50)Copolycarbonate SABIC Innovative (M_(w) = 22,000 g/mol, PS standards)Plastics PC7 PPPBP/BPA (35:65) Copolycarbonate SABIC Innovative (M_(w) =25,000 g/mol, PS standards) Plastics PC8 Transparent PC-siloxanecopolymer SABIC Innovative (M_(w) = 23,000 g/mol, PS standards) PlasticsPC9 Branched PC (M_(w) = 38,000 g/mol, PS SABIC Innovative standards)Plastics PC10 Bisphenol-A based polycarbonate resin Lexan ™ resin, SABIC(M_(w) = 35,000 g/mol, PS standards) Innovative Plastics CYASORB UV-2,2(P-PHENYLEN)DI- CYTEC INDUSTRIES 3638 3,1BENZOXAZIN BV UVA 234 2-(2hydroxy-3,5 dicumyl) Tinuvin 234, Ciba benzotriazole Specialty ChemicalsPCTG Poly(20 mol % ethylene terephthalate)- Eastman Chemical Co. co-(80mol % 1,4- cyclohexanedimethyleneterephthalate) (M_(w) = 70,000 usingpolystyrene standards) PETS Pentaerythritol tetrastearate Lonza, Inc.Pigment Black 7 Printex 85, Monarch 800 DEGUSSA AG, Cabot UVA 5411 2-(2hydroxy-5-t-octylphenyl) Tinuvin 329, Ciba Specialty benzotriazoleChemicals AO1076 Octadecyl (3,5-di-tert-butyl-4- Irganox 1076, Cibahydroxyphenyl)propionate Specialty Chemicals Loxiol EP8578Palmitic/Stearic Acid Ester of COGNIS Dipenta/PentaerythritolOLEOCHEMICALS GMBH PPC-resin Amorphous poly(ester-carbonate), SABICInnovative bisphenol A based poly(phthalate- Plastics carbonate)containing 80% isophthalate- terephthalate ester units (M_(w) = 28,500g/mol, using polystyrene standards) Pigment Blue 60Copolyestercarbonate, known as BASF bisphenol acetone based(poly(phthalate carbonate) containing 60% ester (M_(w) = 28,000 g/mol,PS standards) Solvent violet 36 1,8-Bis[(4-methylphenyl)amino]-9,10-LANXESS, (Macrolex anthracenedione Violet 3R) Solvent Red 135 MACROLEX ™Red EG Lanxess Solvent Yellow 2-Octadecyl-1H-thioxantheno[2,1,9-Clariant, Hostasol Gelb 3G 98 def]isoquinoline-1,3(2H)-dione Vat Red 411H-Thioxantheno[2,1,9- Clariant, Hostasol Red 5Bdef]isoquinoline-1,3(2H)-dione,2- octadecyl Solvent Blue 1041,4-bis(2,4,6-trimethylanilino)- Clariant, Sandoplast Blue anthraquinone2B Solvent Yellow 1,8-Bis(phenylthio)anthraquinone Ciba SpecialityChemicals, 163 ORACET ™ Yellow GHS Copper Copper,(29H,31H-phthalocyaninato(2-)- BASF, Heliogen Blue PhthalocyanineN29,N30,N31,N32)-, (SP-4-1) K7100 Pigment Blue 15:4 Pigment Green 7Cu-Phthalocyanine Halogenated BASF, Heliogen Green K8730 Copper Copper,(29H,31H-phthalocyaninato(2-)- BASF, Heliogen Blue PhthalocyanineN29,N30,N31,N32)-, (SP-4-1)- K6911D Pigment Blue 15:1 Solvent Violet 131-(p-methylaniline)-4-hydroxy Lanxess, Macrolex Violet B anthraquinonePigment Blue 15:4 Copper Phthalocyanine Beta BASF, Heliogen Blue K7104LWSolvent green 28 Macrolex Green G LANXESS Disperse Yellow MACROLEXYELLOW 6G LANXESS 201 Solvent Yellow 93 MACROLEX YELLOW 3G LANXESSPigment Yellow ORACET YELLOW RB Ciba Speciality Chemicals 147 DisperseOrange 47 Macrolex Orange R LANXESS Solvent Red 52 Nacrolex Red 5BLANXESS Solvent orange 63 Hostasol Red GG Clariant Solvent Red 2071,5-Bis(cyclohexylamino)anthraquinone COLOR CHEM Pigment Yellow3,4,5,6-Tetrachloro-N-[2-(4,5,6,7- BASF, Paliotol Yellow K 138tetrachloro-2,3-dihydro-1,3-dioxo-1H- 0961 HDinden-2-yl)-8-quinolyl]phthalimide Phosphonite PEPQ Mixture ofphosphonous acid esters Irgafos PEPQ, Ciba Specialty Chemicals Epoxy3,4-epoxy cyclohexyl methyl-3,4-epoxy Epoxy Resin ERL 4221, cyclohexylcarboxylate Dow Chemical TiO₂ Titanium dioxide KRONOS ™ 2233 KSSpotassium diphenylsulphon-3- SEAL SANDS sulphonate CHEMICALS LTD PTFE &T-SAN 50% Poly(tetrafluoroethylene) + SABIC Innovative 50% E-SANPlastics Antioxidant tris(2,4-di tert.butylphenyl) phosphite Irgafos168, Ciba Specialty Chemicals Phosporic Acid Phosporic Acid diluted withWater to QUARON solution 10% Styrene-acrylate- Joncryl ADR4368S BASFepoxy oligomer Solvent Green 3 MACROLEX ™ GREEN 5B Lanxess AO1010Pentaerythritol tetrakis(3,5-di-tert-butyl- Irganox 1010, Ciba4-hydroxyhydrocinnamate) Specialty Chemicals LaB₆ (lanthanum KHCS-06 TM(pigment dispersion Alconix Europe GmbH hexaboride) master 0.25% LaB₆ inPC) batch in polycarbonate OB Di-(tert.)butyl-benzoxazolyl thiopheneBASF CTO (cesium YMCS-06 TM (pigment dispersion Alconix Europe GmbHtungsten oxide) 1.23% CTO in PC) master batch in polycarbonate PMMAPlexiglas 8N Evonik Degussa GmbH Polystyrene SP256 Supreme Petrochem LTDGrialamid TR55 GRILAMID TR 55 LX (transparent EMS-Grivory thermoplasticpolyamide based on aliphatic and cycloaliphatic blocks)

Example 1

Tables 3 through 7 list formulations and laser marking ability ofsamples produced using the methods and compositions disclosed herein.Each of the samples comprised a first component having a thickness of 1mm and the compositions disclosed in the tables. The results ofComparative Examples 1 to 5 (C1-C5) are illustrated in Table 3, whilethe results for Samples 1 to 5 are illustrated in Table 4. As can beseen from Table 3, C1 exhibited poor interaction with laser light (UVthrough to near infrared), giving an in-homogenous mark. When a smallamount of carbon black was added to the samples as demonstrated in C2 toC5, the interaction with the 1064 nm laser light improved, giving a morehomogenous dark mark as the loading of carbon black was increased via acarbonization process. The addition of carbon black, however, greatlyimpairs the color and transmission levels of visible light and the Tvisas measured according to ASTM D1003. A greyish mark is achieved whenthese parts are irradiated with a UV laser with some increase inreflection and L*, but the mark is much darker when viewed and measuredfrom the rear side through the 1 mm part due to increased absorptionfrom a carbonization type process. The laser light (UV through to nearinfrared) passed through the 1 mm parts and marked or otherwiseintersected with a laser sensitive substrate placed under the parts forC1 to C5.

Surprisingly, Sample 1, comprising a first component having a thicknessof 1 mm, was able to be inscribed with a light mark when laser lightwith a wavelength less than or equal to 500 nm was utilized. Even moresurprising was that in Sample 1, the measured L* and reflection of theUV laser marked areas are more or less the same when viewed and measuredfrom the rear side. Such a characteristic is very desirable in caseswhere the laser mark is applied on the opposite side to the viewingside. Additionally, a laser sensitive substrate placed underneath Sample1 remained unmarked. It was also surprising to discover that theaddition of an organic additive capable of strongly absorbing light atwavelengths less than or equal to 500 nm to give Sample 2, also gave alight colored mark when laser light having a wavelength of less than orequal to 500 nm was utilized. Unlike the addition of carbon black withC2 to C5, in Sample 2, the color and Tvis were essentially unchanged.

The addition of an organic additive capable of strongly absorbing lightat wavelengths less than or equal to 500 nm as in Sample 4 compared toSample 1, improved the contrast and additionally broadened the lasermarking process window by increasing the marking speed. Surprisingly,the combination of small amounts of carbon black to Samples 2 and 4,giving Samples 3 and 5, increased the L* and reflection of the markachieved from a laser with a wavelength less than or equal to 50 nmwithout compromising the color of the mark on the rear side due tocarbonization. In Samples 1 to 5, the interaction between the laser andthe sample was restricted to the first component having a thickness of 1mm. The intense light from the laser did not pass through the firstcomponent and mark the laser sensitive substrate, unlike in C1 to C5,indicating that the inclusion of an organic additive with a strongabsorption of light less than or equal to 500 nm can protect anunderlying substrate from being marked with a laser beam.

Similar trends were seen in the samples displayed in Tables 5 to 7,which included resins such as polystyrene, polyamide, andpolymethylmethacrylate.

TABLE 3 Material C1 C2 C3 C4 C5 PC1 99.65 99.6498 99.649 99.648 99.646PETS 0.3 0.3 0.3 0.3 0.3 Irgafos 168 0.05 0.05 0.05 0.08 0.08 AO1076Pigment Black 7 0.0002 0.001 0.002 0.004 Total 100 100 100 100 100 Tvis88 87 80 72 57 % Transmis- 78 72 62 52 34 sion at 360 nm (%) L* ofsubstrate 5 6 5 4 3 (reflection mode) Average % 0.8 0.6 0.6 0.4 0.3reflection (360-700 nm) substrate 355 nm laser beam marking Substratemarked Yes Yes Yes Yes Yes L* of selected 43 40 47 47 47 mark (frontside) L* of selected 21 19 13 14 12 mark (back side) Delta L* mark 22 2134 33 35 Average % 12.7 11.2 15.4 15.7 15.6 reflection mark (front side)Average % 3.1 2.7 1.6 1.4 1.4 reflection mark (rear side) Delta % 9.68.5 13.8 14.3 14.2 Reflection mark 1064 nm laser beam marking Substratemarked Yes Yes Yes Yes Yes

TABLE 4 Material 1 2 3 4 5 PC1 17.58 99.4 99.3998 17.58 17.58 PC7 8281.75 81.7498 PETS 0.3 0.3 0.05 0.3 0.3 Irgafos 168 0.08 0.05 0.3 0.080.08 AO1076 0.04 0.04 0.04 UVA 5411 0.25 0.25 0.25 0.25 Pigment Black 70.0002 0.0002 Total 100 100 100 100 100 Tvis 89 88 86 88 88 % Transmis-58 2 2 2 2 sion at 360 nm L* of substrate 4 5 4 4 4 (reflection mode)Average % 0.8 0.7 0.4 0.6 0.4 reflection (360-700 nm) substrate 355 nmlaser beam marking Substrate marked No No No No No L* of selected 55 6566 57 58 mark (front side) L* of selected 53 59 61 52 56 mark (backside) Delta L* mark 2 6 5 5 2 Average % 21.1 27.8 33.3 22.7 23.9reflection mark (front side) Average % 19.0 22.9 25.3 18.6 20.7reflection mark (rear side) Delta % 2.1 4.9 8.0 4.1 3.2 Reflection mark1064 nm laser beam marking Substrate marked Yes Yes Yes Yes Yes

TABLE 5 Material C6 C7 C8 6 7 8 9 10 PC6 99.5 99.4998 99.4995 99.25 PC218 18 PETS 0.4 0.4 0.4 0.4 0.3 0.3 AO1076 0.1 0.1 0.1 0.1 0.06 0.06 0.050.05 UVA 5411 0.25 0.25 0.25 PC9 99.65 99.4 PC8 81.94 81.69 PigmentBlack 7 0.0002 0.0005 Total 100 100 100 100 100 100 100 100 Tvis 88 8881 87 85 83 87 87 % Transmission at 360 nm 76 74 72 2 75 2 71 2 L* ofsubstrate 5 4 3 5 6 5 5 5 (reflection mode) Average % reflection 0.6 0.40.5 0.5 0.8 0.6 1.2 0.7 (360-700 nm) substrate 355 nm laser beam marking(95% power) Substrate marked Yes Yes Yes No Yes No Yes No L* of selectedmark (front side) 38 41 43 67 38 61 36 54 L* of selected mark (backside) 22 16 15 61 28 55 24 50 Delta L* mark 16 25 28 6 10 6 12 4 Average% reflection mark 9.7 11.7 12.6 33.7 9.9 27.3 10.5 21.9 (front side)Average % reflection mark 3.3 2.1 1.8 25.3 5.4 20.4 5.9 19.4 (rear side)Delta % Reflection mark 6.4 10 11 8.4 4.5 6.8 4.6 2.5 1064 nm laser beammarking (95% power) Substrate marked Yes Yes Yes Yes Yes Yes Yes Yes

TABLE 6 Material C9 11 12 13 14 15 PC3 99.61 99.36 PETS 0.3 0.3 0.3 0.30.3 0.3 Epoxy 0.03 0.03 0.03 0.03 0.03 0.03 Phosphonite 0.06 0.06 0.060.06 0.06 0.06 PEPQ UVA 5411 0.25 0.25 0.25 PC4 99.61 99.36 PPC-resin99.61 99.36 Total 100 100 100 100 100 100 Substrate Yes No No No No Nomarked Tvis 89 90 89 89 91 84 % Transmis- 74 2 51 2 38 1 sion at 360 nmL* of substrate 7 7 4 4 14 14 (reflection mode) Average % 0.8 0.8 0.50.4 2.1 1.7 reflection (360-700 nm) substrate 355 nm laser beam markingL* of selected 43 62 52 59 55 60 mark (front side) L* of selected 36 5849 58 50 56 mark (back side) Delta L* mark 7 4 3 1 5 4 Average % 12.828.0 18.9 24.0 21.3 25.8 reflection mark (front side) Average % 8.3 22.815.3 21.2 16.9 20.9 reflection mark (rear side) Delta % 4.5 5.3 3.6 2.84.5 4.9 reflection mark 1064 nm laser beam marking Substrate Yes Yes YesYes Yes Yes marked

FIGS. 2, 3, and 4 illustrate scanned images of C1, C2, and C3,respectively. The samples were laser inscribed with a 1064 nm laserbeam. The 1 mm parts were placed on a white background to emphasizecontrast with the lower images in each of the figures showing the effect(i.e., inhomogeneous interaction) of lowering the line spacing from 0.05mm to 0.03 mm

TABLE 7 Material C10 C11 C12 16 17 18 Grialamid TR55 100 90.6 PMMA 10090.6 Polystyrene 100 90.6 CYASORB UV-3638 0.4 0.4 0.4 Total 100 100 100100 100 100 Tvis 92 92 90 88 92 86 % Transmission at 360 nm 34 38 82 9 32 L* of substrate (reflection 4 4 5 4 4 5 mode) Average % reflection 0.50.4 0.6 0.5 0.5 0.5 (360-700 nm) substrate 355 nm laser beam marking(95% power) Substrate marked No No Yes No No No L* of selected mark — —38 61 63 48 (front side) L* of selected mark — — 23 58 58 44 (back side)Delta L* mark — — 15 3 5 3 Average % reflection mark — — 9.9 28.4 29.715.8 (front side) Average % reflection mark — — 3.7 23.1 23.8 12.3 (rearside) Delta % reflection mark — — 6.3 5.3 5.9 3.5 355 nm laser beammarking (85% power) L* of selected mark — — — 58 64 51 (front side) L*of selected mark — — — 53 60 47 (back side) Delta L* mark — — — 5 4 4Average % reflection mark — — — 24.7 31.6 18.1 (front side) Average %reflection mark — — — 18.7 25.1 15.5 (rear side) Delta % reflection mark— — — 6.0 6.5 3.5 355 nm laser beam marking (75% power) L* of selectedmark — — — 43 61 38 (front side) L* of selected mark — — — 37 59 23(back side) Delta L* mark — — — 6 2 15 Average % reflection mark — — —12.4 28.0 9.9 (front side) Average % reflection mark — — — 8.5 24.3 3.7(rear side) Delta % reflection mark — — — 3.9 3.7 6.3 1064 nm laser beammarking Substrate marked Yes Yes Yes Yes Yes Yes

Example 2

In this example, the effect of different additives on the samples wasobserved. As seen in C2 to C5, carbon black can be used to enhance theinteraction of compositions with laser light to improve the dark markcontrasts (i.e., carbonization). However, the addition of low levels ofcarbon black can greatly lower the Tvis as measured according to ASTMD1003-00 described above and can lead to little improvement in the colorcontrast and inscription processing parameters when compared withorganic absorbing additives (compare C2 to C5 with Samples 1 to 5). Thesamples in Tables 8 to 11 illustrate that light colored, reflectivemarks with little or no carbonization can be achieved across a widerange of concentration types and combinations.

Inorganic additives such as lanthanum hexaboride (LaB₆) or Cesiumtungsten oxide (CTO) can also be used to enhance the interaction ofcompositions with laser light and improve mark contrasts. As can be seenin Table 11, the addition of low loadings of these additives did notdramatically lower the Tvis. However, C20 to C26, compositions basedsolely on these additives, exhibited little improvement in the color asit is believed that carbonization dominates and yields a dark mark. Thecontrast from the front and back was lower as compared to Samples 34 and35, which also contained a small amount of a UV absorbing additive. L*of the front side and back side was also much lower for C20 to C26compared to Samples 34 and 35. Surprisingly the combination or organicabsorbing additives with inorganic absorbing additives such as LaB₆ orCTO, which are also capable of strongly absorbing light as wavelengthsless than or equal to 500 nm, such as in Samples 34 and 35, gave lightmarks and lower profiles compared with when the organic additives wereused alone. The combinations also allowed the generation of light anddark marks in the same composition by changing laser wavelength.

FIG. 5 illustrates Sample 22 that was laser inscribed with a 355 nmlaser beam. The 2.5 mm thick part was placed on a black background toemphasize contrast. FIG. 6 illustrates a scan of the laser inscriptionson Sample 22 in transmission mode including text and bar codes (leftimage). The same Quick Response Matrix Barcode (QR code) was inscribedas a watermark in the dotted area and was not visible when scanned. Theright image in FIG. 6 was an optical image obtained by using amicroscope of a magnified part of the QR code viewed in transmissionmode. FIG. 7 is a scanning electron microscope image (×1500magnification) of the marked square 30 in the lower left hand corner ofthe matrix of Sample 22 as illustrated in FIG. 5. The thermal effect ofthe process can be seen from this image.

TABLE 8 Material C13 C14 C15 19 20 21 22 23 AO1076 0.05 0.05 0.05 0.050.05 0.05 0.05 0.05 UVA 5411 0.001 0.005 0.01 0.05 0.1 0.15 0.3 0.6 PETS0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 PC6 99.52 99.51 99.51 99.47 99.42 99.3799.22 98.92 Pigment Blue 60 0.0109 0.0109 0.0109 0.0109 0.0109 0.01090.0109 0.0109 Solvent violet 36 0.0153 0.0153 0.0153 0.0153 0.01530.0153 0.0153 0.0153 Total 100 100 100 100 100 100 100 100 Tvis 89 89 8989 89 89 89 89 % Transmission at 68 48 31 4 2 2 2 2 360 nm L* ofsubstrate 6 5 5 4 4 6 5 5 (reflection mode) Average % 0.7 0.5 0.5 0.40.4 0.6 0.5 0.5 reflection (360-700 nm) substrate 355 nm laser beammarking (95% power) Contrast front 105 111 114 118 138 148 138 124Contrast back 54 77 78 100 116 132 127 122 Delta contrast 51 34 36 18 2216 11 2 Speed (mm/sec) 600 600 600 675 750 975 1125 1125 L* of selectedmark 44 45 46 56 60 62 61 59 (front side) L* of selected mark 23 24 2846 54 57 56 55 (back side) Delta L* mark 21 21 18 10 6 4 5 4 Average %13.5 14.3 14.9 22.4 26.1 28.2 27.6 24.9 reflection mark (front side)Average % 2.7 3.8 5.0 11.5 19.4 18.3 19.2 19.6 reflection mark (rearside) Delta % Reflection 10.8 10.4 9.9 10.9 6.7 9.8 8.4 5.3 mark 355 nmlaser beam marking (85% power) Contrast front — — — 133 140 146 138 130Contrast back — — — 104 121 130 129 125 Delta contrast — — — 29 19 16 95 355 nm laser beam marking (75% power) Contrast front — — — 108 150 153143 137 Contrast back — — — 89 132 138 132 131 Delta contrast — — — 1918 15 11 6

TABLE 9 Material C16 C17 24 25 26 27 28 AO1076 0.05 0.05 0.05 0.05 0.050.05 0.05 UVA 234 0.0005 0.005 0.05 0.1 0.15 0.3 0.6 PETS 0.4 0.4 0.40.4 0.4 0.4 0.4 PC6 99.5233 99.5188 99.4738 99.4238 99.3738 99.223898.9238 Pigment Blue 60 0.0109 0.0109 0.0109 0.0109 0.0109 0.0109 0.0109Solvent violet 36 0.0153 0.0153 0.0153 0.0153 0.0153 0.0153 0.0153 Total100 100 100 100 100 100 100 Tvis 89 89 89 89 89 89 89 % Transmission at67 43 3 2 2 2 2 360 nm L* of substrate 4 5 3 4 3 4 3 (reflection mode)Average % reflection 0.5 0.6 0.4 0.4 0.3 0.4 0.3 (360-700 nm) substrate355 nm laser beam marking (95% power) Contrast front 106 109 119 152 135139 127 Contrast back 56 68 101 126 113 129 120 Delta contrast 50 41 1826 22 10 7 Speed (mm/sec) 600 600 675 750 975 1050 1125 L* of selectedmark 44 45 55 60 60 60 60 (front side) L* of selected mark 22 25 47 5655 56 56 (back side) Delta L* mark 22 20 8 4 5 4 5 Average % reflection13.2 14.0 22.2 26.4 26.8 26.2 26.3 mark (front side) Average %reflection 2.9 3.9 14.7 20.8 19.0 18.2 18.9 mark (rear side) Delta %Reflection 10.3 10.2 7.5 5.5 7.8 8.0 7.4 mark 355 nm laser beam marking(85% power) Contrast front — — 131 143 140 137 126 Contrast back — — 110126 128 130 124 Delta contrast — — 21 17 12 7 2 355 nm laser beammarking (75% power) Contrast front — — 124 146 147 143 135 Contrast back— — 102 130 131 136 128 Delta contrast — — 22 16 16 7 7

TABLE 10 Material C18 C19 29 30 31 32 33 AO1076 0.05 0.05 0.05 0.05 0.050.05 0.05 CYASORB UV-3638 0.0005 0.005 0.05 0.1 0.15 0.3 0.6 PETS 0.40.4 0.4 0.4 0.4 0.4 0.4 PC6 99.52 99.51 99.47 99.42 99.37 99.22 98.92Pigment Blue 60 0.0109 0.0109 0.0109 0.0109 0.0109 0.0109 0.0109 Solventviolet 36 0.0153 0.0153 0.0153 0.0153 0.0153 0.0153 0.0153 Total 100 100100 100 100 100 100 Tvis 89 89 89 89 89 89 89 % Transmission at 360 nm65 30 2 2 2 2 2 L* of substrate (reflection 4 5 3 5 3 6 8 mode) Average% reflection (360-700 nm) 0.5 0.6 0.3 0.6 0.4 0.6 0.8 substrate 355 nmlaser beam marking (95% power) Contrast front 106 113 139 154 141 138126 Contrast back 52 74 114 129 129 123 119 Delta contrast 54 39 25 2512 15 7 Speed (mm/sec) 600 600 750 825 1050 1125 1312 L* of selectedmark (front 44 45 60 63 63 62 58 side) L* of selected mark (back 22 2654 58 58 57 57 side) Delta L* mark 22 19 6 5 5 5 1 Average % reflectionmark 13.6 14.4 26.1 29.1 29.1 27.8 24.3 (front side) Average %reflection mark 3.3 4.4 19.1 22.5 21.9 21.0 20.3 (rear side) Delta %reflection mark 10.3 10.0 6.9 6.6 7.1 6.8 4.0 355 nm laser beam marking(85% power) Contrast front — 103 150 157 148 141 135 Contrast back — 57130 139 133 132 126 Delta contrast — 46 20 18 15 9 9 355 nm laser beammarking (75% power) Contrast front — — 158 161 150 145 148 Contrast back— — 135 141 138 140 144 Delta contrast — — 23 20 12 5 4

TABLE 11 Material C20 C21 C22 C23 C24 C25 C26 34 35 PC6 99.52 99.4798.52 98.02 98.52 98.02 97.52 97.72 98.22 PETS 0.4 0.4 0.4 0.4 0.4 0.40.4 0.4 0.4 CYASORB UV- 0.3 0.3 3638 AO1076 0.05 0.05 0.05 0.05 0.050.05 0.05 0.05 0.05 Pigment Blue 60 0.0109 0.0109 0.0109 0.0109 0.01090.0109 0.0109 0.0109 0.0109 Solvent violet 36 0.0153 0.0153 0.01530.0153 0.0153 0.0153 0.0153 0.0153 0.0153 CTO MB in PC 1 1.5 2 1.5 LaB₆MB in PC 0.05 1 1.5 1 Total 100 100 100 100 100 100 100 100 100 Tvis 9088 85 83 90 89 89 90 85 % Transmission at 78 67 57 48 73 69 65 2 2 360nm L* of substrate 6 5 5 5 5 4 5 6 9 (reflection mode) Average % 0.7 0.70.7 0.7 0.6 0.5 0.6 0.6 1.0 reflection (360-700 nm) substrate 355 nmlaser beam marking (95% power) Contrast front 98 88 92 104 90 101 103165 169 Contrast back 56 32 17 18 41 31 31 143 129 Delta contrast 42 5675 86 50 70 71 22 39 L* of selected mark 32 44 45 45 43 43 45 67 66(front side) L* of selected mark 20 13 12 13 15 16 16 62 58 (back side)Delta L* mark 12 31 33 32 28 27 29 5 8 Average % 6.9 13.4 14.0 14.3 12.613.1 14.2 34.5 32.5 reflection mark (front side) Average % 3.0 1.5 1.51.6 1.8 2.1 2.2 26.5 20.9 reflection mark (rear side) Delta % reflection3.9 11.9 12.5 12.7 10.8 11 12 8 11.6 mark 355 nm laser beam marking (85%power) Contrast front — 89 91 92 96 96 95 175 176 Contrast back — 24 1520 34 34 34 151 134 Delta contrast — 65 76 73 63 62 61 24 42 355 nmlaser beam marking (75% power) Contrast front — 74 88 89 54 58 73 176178 Contrast back — 15 21 22 27 22 25 148 134 Delta contrast — 60 67 6728 36 48 28 44

FIG. 9 is a photographic image of Sample 35 showing a light mark on aRAL 9010-GL background, where the mark was created using a laser beamhaving a wavelength of less than 500 nm and a dark mark on a RAL 9005-GLbackground, created using a laser beam having a wavelength of 1064 nm.

Example 3

In this example, Samples 13, 25, 30, 32, 34, and 35 were tested forprofile height and compared to the profile height of C1 to C5. Theaverage profile of the mark was measured in micrometers. As can be seenin Table 12, the average profile of the marks generated from treatingthermoplastics with laser light having a wavelength of less than 500 nmwas surprisingly low with lightest colored, most reflective marksexhibiting profiles less than 30 micrometers. The profiles of the dark,carbonized marks of C1 and C2 are much higher. In C3 to C5, where afoaming type process beings to take effect and the mark becomes a browncolor from the front, (but is much darker when viewed from the rear sidedue to contribution from the carbonization process), the profile is morethan double compared with laser light having a wavelength of less than500 nm.

The profile is lower when such a light mark is not required and can berendered to be less than 5 micrometers to generate a watermark.Watermarks that are visible only under certain angles can be achievedwith profiles rendered to be less than 2 micrometers.

TABLE 12 355 nm laser beam marking Laser Profile power #13 #25 #30 #32#34 #35 Average 95% 15.4 14.5 14.9 12.9 11.2 9.0 height of best 85% 14.913.3 18.9 14.1 11.2 11.1 contrast 75% 13.7 11.9 19.0 11.9 11.7 11.7 mark(microm- eters) 1064 nm laser beam marking Laser C. Ex. C. Ex. C. Ex.C-Ex. C. Ex. Profile power #1 #2 #3 #4 #5 — Average 95% 104.8  80.3 59.470.9 73.2 — height of best contrast mark (microm- eters)

Example 4

Tables 13 and 14 demonstrate the process whereby materials can be laserwelded with laser light having a wavelength longer than 800 nm and boththe upper and lower joined parts are laser inscribed with laser lightlower than 800 nm, specifically, less than 500 nm FIG. 10 is aphotographic image of Sample 36 laser welded to Sample 40 using a laserbeam having a wavelength of 960 nm. The samples have been laser markedwith a laser beam having a wavelength of 355 nm. The image on the leftis the laser on the lower part (Sample 40), while the image on the rightis the laser mark on the upper part (Sample 36).

TABLE 13 Material 36 37 38 39 40 PC1 99.37 97.86 96.38 97.94 97.79Loxiol EP8578 0.4 0.4 0.4 0.3 0.4 AO1076 0.05 0.05 0.05 0.036 0.05AO1076 0.02 UVA 5411 0.15 0.15 0.15 0.3 0.25 LaB₆ MB in PC 1.5 1.5 1.40.75 CTO MB in PC 0.75 Pigment Black 7 0.0007 0.003 Solvent Red 1350.021 0.5 Solvent Yellow 98 0.01 Vat Red 41 0.006 TiO₂ 0.65 SolventYellow 163 0.37 0.002 Pigment Yellow 138 0.01 Pigment Blue 60 0.0109Solvent violet 36 0.0153 Total 100 100 100 100 100 Laser absorbing > NoYes Yes Yes Yes 800 nm Laser absorbing < Yes Yes Yes Yes Yes 500 nmLaser welding U L L L L geometry. Upper (U: laser transparent) or lowerpart (L: laser absorbing) Part marked with Yes Yes Yes Yes Yes 355 nmlaser beam

TABLE 14 Material 41 42 43 44 PC1 37.95 37.60 33.90 33.96 PC2 38.2638.31 PC3 40.00 40.00 PCTG 24.78 24.78 PETS 0.30 0.30 0.30 0.30Phosphonite PEPQ 0.09 0.09 PC5 22.20 22.20 KSS 0.30 0.30 PTFE & T-SAN0.30 0.30 Antioxidant 0.09 0.09 Phosporic Acid solution 0.05 0.05Styrene-acrylate-epoxy oligomer 0.25 0.25 UVA 5411 0.25 0.25 UVA 2340.30 0.30 AO1010 0.12 0.12 Solvent Green 3 0.13 Solvent Red 135 0.13Pigment Black 7 0.30 0.20 Solvent violet 36 0.30 Solvent Blue 104 0.30Total 100 100 100 100 Laser absorbing > 800 nm Yes No No Yes Laserabsorbing < 500 nm Yes Yes Yes Yes Laser welding geometry. L U U L Upper(U: laser transparent) or lower part (L: laser absorbing) Part markedwith 355 nm Yes Yes Yes Yes laser beam

Example 5

Tables 15 to 18 demonstrate that colorants generally used to modulatethe visible color of compositions can themselves contribute to theinteraction of the compositions with laser light having a wavelength ofless than 500 nm to give light colored marks. Achieving a light coloredmark on a transparent or amorphous material (essentially non-reflecting)offers the possibility to tune the substrate color in a traditionalmanner. The addition of absorbing additives including, but not limitedto, hydroxybenzophenones, hydroxybenzotriazoles, hydroxybenzotriazines,cyanoacrylates, oxanilides, benzoxazinones, benzylidene malonate type UVstabilizers (e.g., Samples 46, 48, 50, 52, and 54) allows the color ofthe laser mark to be modified. The substrate color and the color of themark can be determined by the choice of colorant and surprisingly, canbe further manipulated by the addition of an organic additive, includingcarbon black (compare e.g., Samples 61 and 63 with Samples 62 and 64,respectively), capable of strongly absorbing light at wavelengths lessthan or equal to 500 nm

TABLE 15 Material 45 46 47 48 PC1 99.45 99.2 99.485 99.235 Antioxidant0.05 0.05 0.05 0.05 PETS 0.3 0.3 0.3 0.3 UVA 5411 0.25 0.25 SolventGreen 3 0.1 0.1 Solvent Red 135 0.1 0.1 Pigment Blue 15:4 0.11 0.11Macrolex Violet 3R 0.055 0.055 Total 100 100 100 100 Absorption at 360nm (%) 1 1 1 1 Average reflection 0.0 0.0 0.1 0.0 (360-700 nm) substrate(%) 355 nm laser beam marking (95% power) L* of substrate 2 1 6 6(reflection mode) a* of substrate 1.1 1.0 15.2 15.1 b* of substrate 0.70.5 −13.8 −13.7 L* of selected marks 44 49 45 53 a* −0.5 −0.5 1 0.4 b*0.5 −0.4 6.4 6.2 Delta L* (mark − 42 48 39 47 substrate)

TABLE 16 Material 49 50 51 52 53 54 PC1 99.553 99.303 99.5381 99.288199.48822 99.23822 Antioxidant 0.05 0.05 0.05 0.05 0.05 0.05 PETS 0.3 0.30.3 0.3 0.3 0.3 UVA 5411 0.25 0.25 0.25 Solvent Green 3 0.0308 0.03080.0462 0.0462 Solvent Red 135 0.066 0.066 Solvent Blue 104 0.0001 0.00010.00015 0.00015 Solvent Yellow 93 0.0508 0.0508 0.0702 0.0702 SolventRed 52 0.0289 0.0289 0.0433 0.0433 Pigment Black 7 0.005 0.005 0.00130.0013 0.00193 0.00193 Pigment Blue 15:4 Macrolex Violet 3R 0.026 0.026Total 100 100 100 100 100 100 L* of substrate (reflection 3 3 1 1 1 1mode) a* of substrate 4.5 4.4 0.4 0.1 0.5 0.1 b* of substrate 0.9 0.90.3 0.1 0.2 0.0 Average % reflection substrate 0.2 0.2 0.0 0.0 0.1 0.0(360-700 nm) 355 nm laser beam marking (95% power) L* of selected marks49 57 54 56 56 55 a* 3.6 3.4 0.9 −0.3 7 −0.3 b* 8 5.5 7.2 2.4 7.8 2.7Delta L* (mark − substrate) 46 54 53 55 55 54

TABLE 17 Material 55 56 57 58 59 60 PC8 82.8 82.8 82.8 82.8 82.8 82.8AO1076 0.06 0.06 0.06 0.06 0.06 0.06 PC2 6 6 6 6 6 6 UVA 5411 0.2 0.20.2 0.2 0.2 0.2 9105 10.69 10.69 10.658 10.775 10.776 10.848 SolventGreen 3 0.125 Solvent Red 135 0.125 0.18 0.018 0.009 Solvent violet 360.25 0.09 0.055 0.075 0.065 Pigment Yellow 138 0.012 Pigment Blue 15:40.11 Solvent Violet 13 0.071 Copper Phthalocyanine Pigment Blue 0.01815:1 Total 100 100 100 100 100 100 L* of substrate (reflection mode) 4 37 6 5 3 a* of substrate 0.7 0.4 2.0 13.9 0.8 1.1 b* of substrate −1.5−2.7 −1.5 −14.4 −3.1 −3.1 Average % reflection substrate (360-700 nm)0.5 0.6 1.1 1.3 0.5 1.9 355 nm laser beam marking (95% power) L* ofselected marks 50 47 47 55 50 54 a* −0.7 2.9 3.3 0.7 1.7 0.6 b* 0.2 −3.30.6 5.6 −2.3 −0.8 Delta L* (mark − substrate) 46 44 40 49 45 50 Delta a*−1.4 2.5 1.3 −13.2 0.9 −0.5 Delta b* 1.7 −0.6 2.1 20.0 0.8 2.3 Average %reflection mark 18.1 17.7 17.3 22.2 19.7 21.8 Delta % reflection mark17.6 17.1 16.1 20.8 18.8 21.3

TABLE 18 Material 61 62 63 64 PC8 82.8 82.8 82.8 82.8 AO1076 0.06 0.060.06 0.06 PC2 6 6 6 6 UVA 5411 0.2 0.2 0.2 0.2 9105 10.848 10.838 10.59810.588 Solvent Red 135 0.066 0.066 Solvent violet 36 0.026 0.026 PigmentYellow 138 0.3 0.3 Pigment Black 7 0.01 0.01 Copper Phthalocyanine 0.0260.026 Pigment Blue 15:4 Pigment Green 7 0.016 0.016 Total 100 100 100100 L* of substrate 12 4 20 15 (reflection mode) a* of substrate 3.2 1.9−22.2 −5.0 b* of substrate −1.0 −1.8 12.5 4.6 Average % 1.9 0.5 2.2 1.8reflection substrate (360-700 nm) 355 nm laser beam marking (95% power)L* of selected mark 54 59 61 57 a* 2.1 2.6 −6.1 −2.9 b* 1.3 5.8 16.914.2 Delta L* (mark − 42 55 41 42 substrate) Delta a* −1.0 0.7 16.1 2.1Delta b* 2.2 7.6 4.3 9.6 Average % reflection mark 22.4 26.1 25.9 23.0Delta % reflection mark 20.5 25.6 23.7 21.3

Surprisingly it was discovered that laser light with wavelengths lessthan or equal to 500 nm can interact with the compositions disclosedherein by a thermal mechanism to give light colored markings. Forexample, the light colored markings can be white (e.g., white, offwhite, bright white ivory, snow, pearl, antique white, chalk, milkwhite, lily, smoke, seashell, old lace, cream, linen, ghost white,beige, cornsilk, alabaster, paper, whitewash, etc.). By modulating thecompositions and the method of marking, the inscriptions can be madevisible to nearly visible. The combination of the method andcompositions can allow text, logos, two dimensional-data matrices, andimages to be inscribed in compositions such as polycarbonate,bisphenol-A polycarbonate based copolymers, polyesters, PMMA,polystyrene, polyamides, and combinations comprising at least one of theforegoing. The markings (e.g., dots) can be assembled to generate twodimensional data matrices and images of varying size and clarity bymanipulating the laser process. Applications can include identificationcards (e.g., license, passport, etc.). Additionally, semi-covertinscriptions can be customized to provide logos, text, and machinereadable data on various components made from the compositions describedherein. Applications can include data and images on identificationcards, security and authentication data on phones, computers, andautomotive glazing, and logs on televisions, etc.

The following examples of compositions for UV active laser inscriptionswere prepared using the materials of Table 2. The thermoplastic testspecimens were prepared by melt extrusion on a Werner & Pfleiderer 25 mmtwin screw extruder, using a nominal melt temperature of 290 to 310° C.,25 inches (635 mm) of mercury vacuum and 450 rpm. The extrudate waspelletized and dried at 110° C. for 3 hours. Test specimens wereproduced from the dried pellets and were injection molded at nominaltemperatures of 290 to 320° C.

A Trumark 6330 laser (355 nm), which has a power output of 2 Watts (W),was used to inscribe the test pieces with a processing matrix consistingof a range of laser conditions such as frequency of 20 to 40 kiloHertz(kHz), speed of 600 to 1800 millimeters per second (mm/sec), and a fillfactor of 0.03 to 0.45 mm, i.e., the spacing between adjacent lines oflaser dots. The settings were not further optimized and merely indicatethe ability to control the intensity of the visible legibility and UVactivity by modifying the laser parameters.

A transparent thermoplastic BPA based co-polymer composition comprisedof PPPBP/BPA copolycarbonate (Ex. No. 66 of Table 19) interacts with UVlaser light to give UV active laser mark while Sample No. 65 exhibitedno UV activity (fluorescence) in the area treated with the laser. Theaddition of UV absorbing additive or colorant to the formulation ofsample No. 65 to give Sample No. 67 and other polycarbonate or BPA basedcopolymers based compositions yields UV active laser inscribedmicrodots. The visibility or legibility of the microdot arrangements canbe tuned from clearly legible to semi-covert or barely visible bymodulating the level of interaction and hence the degree of scatteringby the physical size/shape of the resulting microdot (FIG. 4).

FIG. 11 illustrates a laser inscribed 2.5 mm thick sample of 69 of Table19 placed on a black background to illustrate color and contrast ofmark. The visibility of the array of microdots varies from clearlyvisible to semi-covert or barely visible depending on the laserparameters & process. The insets are the indicated regions viewed underUV illumination under an optical microscope. As shown in FIG. 11, thelaser inscribed microdots are visible under UV illumination (i.e., UVactive), and, surprisingly, it was found that the intensity of the UVresponse of the laser-inscribed microdots could be modulated by changingthe laser parameters such as power, frequency, speed, line spacing,focus. FIG. 14 shows a laser inscribed barcode on example 70 from Table19 viewed under a black light on a white background. The white mark isvisible at an angle, but under UV illumination the laser treated area isdirectly visible.

In contrast, compositions such as PMMA, polystyrene and polyamide(Sample Nos. 71-73 of Table 21) also give visible microdots uponaddition of an absorbing additive or colorant due to the scattering ofthe visible light by the microdots, but they are not UV active

TABLE 19 Transparent thermoplastic BPA & BPA based co-polymercompositions Sample No. 65 66 67 68 69 70 PC1 99.65 17.58 99.4 16.1 PC782 PETS 0.3 0.3 0.3 0.4 0.4 AO1076 (205) Irgafos 168 0.05 0.08 0.05 0.050.05 0.06 AO1076 0.04 UVA 5411 0.25 0.3 0.3 PC6 99.55 99.25 PC8 83Pigment Blue 60 0.0109 0.0109 0.0109 Solvent violet 36 0.0153 0.01530.0153 Sum 100 100 100 100 100 100 Visible laser inscription NO YES YESNO YES YES UV active laser inscribed NO YES YES NO YES YES microdots %Transmission at 355 nm 78 58 <2 77 <2 <2

TABLE 20 Transparent thermoplastic compositions without BPA based(co)polymers Sample No. 71 72 73 Grialamid TR55 90.6 PMMA 90.6Polystyrene 90.6 CYASORB UV-3638 (2309) 0.4 0.4 0.4 Sum 100 100 100Visible laser inscription YES YES YES UV active laser inscribedmicrodots NO NO NO % Transmission at 355 nm 9 3 2

The following examples were prepared using a laser having a wavelengthof 355 nm and z-axis offset of 8 mm above the surface. A Trumark 6330laser (355 nm), which has a power output of 2 Watts (W) was used toinscribe the test pieces with a processing matrix consisting of a rangeof laser conditions such as frequency of 27 to 32 kiloHertz (kHz),velocity of 834 to 975 millimeters per second (mm/sec), and a linespacing of 0.03 mm, margin spacing of 0 mm, hatching angle of 90degrees, and 1 hatching. The power setting was 95% unless otherwisestated.

TABLE 21 Item Code Item Description Unit A B C D E F 205 Irgafos 168 %0.06 0.06 0.06 0.06 0.06 0.06 235 UVA 5411 % 0.3 3990 PC masterbachlanthanum % 2 hexaboride 07183 0.1% pigment black 7 in PC % 0.79 0.759175 PC2 % 34.94 32.94 34.15 34.19 6.05 19.94 9135 PC10 % 65 65 65 65 65669 PC8 % 82.59 9105 PC1 % 11 TiO2 % 15 100 100 100 100 100 100Thickness mm 100 50 100 50 200 100

The various examples were constructed with the materials listed in Table21. The letters A-F represent a material used as a layer in themultilayered article. In the following examples, the layers were joinedtogether through a lamination process.

Sample No. 75 (monolayer A) exhibited little interaction with laserlight having a wavelength of 355 nm. However As shown in Table 22,However the addition of 10 ppm or less of carbon black to sample No. 75to give sample No. 74, a dark black mark is achieved using a laserhaving a wavelength of 355 nm and z-axis offset of 8 mm above thesurface of sample No. 74 (of Table 21), a composition with weak UVA. Theinscription is particularly darker when the mark is viewed and measuredon the opposite to the laser interaction (Bottom). Sample 75 comprises apolycarbonate layer (material A of Table 21) without UVA (UVtransparent) laminated to the identical construction of sample No. 74.As illustrated in Table 22, the L* for Sample 75 was lower on the sidewith laser interaction, indicating that a darker mark was achieved whena UV transparent layer is laminated on top of a UVA layer. Accordingly,a multilayer construct of visibly transparent sections comprised of atleast two layers, one of which has little UVA and exhibits minimalinteraction with laser light less than 500 nm (UV transparent), adjoinedto another layer with weak UVA gives a deep, dark laser mark. As usedherein, a UV transparent layer is a layer that has a transmission ofabout 90% or greater. A white mark can be generated by laminatinganother visibly transparent film with strong UVA below the section withweak UVA. Thus, both black and white marks can be generated in thetransparent article regardless of the substrate composition orsensitivity to UV light. For example, a black and white image can beachieved by treating a construct exemplified by Sample 76 the sectionwith strong UVA with a laser light less than 500 nm to produce the lightcolored mark while directing the laser towards the weak UVA section,optionally covered with a UV transparent section.

TABLE 22 Sample No. 74 #74 Top Bottom #75 #76 Spec Inc. (mark) L* 39.728.9 78.3 29.5 a* 0.5 0.4 −0.2 0.4 b* 3.5 0.6 3.1 1.2 Spec Exc. (mark)L* 37.5 11.2 76.2 13.7 a* 0.5 0.9 −0.2 0.8 b* 3.9 2.4 3.1 2.7 ConstructA A C C C E

Sample No. 77 of Table 23 demonstrates that a thin film with strong UVA(material E) substantially protects a substrate containing a highloading of titanium dioxide (material F) that would normally exhibitstrong interaction when exposed directly with laser light less than 500nm

TABLE 23 Sample 77 Substrate color Spec Inc. L* 91.1 a* −0.7 b* 0.3 SpecExc. (mark) L* 88.9 a* −0.7 b* 0.3 Construct E F

Sample Nos. 78-84 of Table 24 demonstrate various constructionscomprising several combinations and arrangements of layers or sectionswith tuned UV absorption/transparency. The color of the combinations inTable 25 indicates that these films or sections have little impact onthe color of the assembly. Each construction exhibits exceptionally darkmarks on a white substrate (material F) with laser light having awavelength less than 500 nm.

TABLE 25 Sample 78 79 80 81 82 83 84 delamination Yes Yes No No Yes NoNo Substrate color Spec Inc. L* 91.4 91.5 91.6 91.6 91.5 91.0 90.8 a*−0.6 −0.8 −0.6 −0.6 −0.6 −0.4 −0.4 b* −0.4 −0.5 −0.7 −0.8 −0.4 −0.5 −0.5Spec Inc. (mark) L* 31.5 29.7 30.6 29.5 31.2 31.4 31.1 a* 0.2 0.4 0.40.6 0.3 0.3 0.4 b* 1.1 1.8 1.3 2.7 1.3 1.0 1.4 Spec Exc. (mark) L* 14.614.9 15.8 17.4 14.9 17.0 16.7 a* 0.6 0.7 0.8 0.8 0.6 0.5 0.6 b* 3.2 3.33.4 3.6 3.3 2.7 3.2 Construct A (x1) A (x1) A (x3) A (x4) A (x1) A (x3)A (x4) C B B B D D D E E E E E E E F F F F F F F

The colored substrates listed in Table 26 were subjected to IR laser(1064 nm) and an UV laser (355 nm). Marking the substrate with the IRlaser resulted in browning, greying, and barely visible marks. Thecolored substrates were covered with additional layers A (UVtransparent), C (weak UVA), and E (strong UVA). The combination andarrangement of the additional layers or sections with tuned UVabsorption/transparency gave exceptionally dark marks with neutral a*,b* tones (close to zero) with laser light having a wavelength less than500 nm. The consistency of the mark across the range of colors isevidenced by the narrow spread of L*, a* and b* values listed in Table27 and Table 28. As shown in FIGS. 12 and 13, a darker mark was formedin Sample No. 80 when a transparent layer was employed. Table 27illustrates the results of the various constructs and laser wavelengthswith Spectralon Included. Table 28 illustrates the results of thevarious constructs and laser wavelengths with Spectralon Excluded. Asused in Tables 27 and 28, “Rofin” refers to the “Rofin Powerline E”laser with a track width of 0.084 mm, 27 ampere, a velocity of 300 mm/s,a pulse frequency of 10000 Hz, line spacing 0.084 mm, margin spacing 0mm, hatching angle of 45 degrees and 1 hatch.

TABLE 26 red pink green light green blue yellow Sample No. 85 86 87 8889 90 83 83 83 83 83 83 15.339 16.308 14.8774 15.3957 15.3833 15.0860.06 0.06 0.06 0.06 0.06 0.06 pigment black 7 0.0003 0.001 TiO2 1.5 0.51.9 1.5 1.5 1.8 Solvent Blue 104 0.0017 Pigment Blue 15:4 0.009 0.00110.014 Solvent green 28 0.0002 Disperse Yellow 201 0.148 0.042 SolventYellow 93 0.005 0.027 Pigment Yellow 147 Solvent Yellow 163 0.0005 0.027Disperse Orange 47 0.015 0.007 Solvent Red 52 0.0003 0.0005 Vat Red 410.05 0.05 Solvent orange 63 0.036 0.06 Solvent Red 207 0.015 OB 0.04 Sum100 100 100 100 100 100

TABLE 27 Spec Inc. Sample Construct 85 86 87 88 89 90 Max Min SpreadSubstrate color L* 60.3 71.3 80.5 88.4 77.1 90.6 a* 61.9 58.6 −37.4−24.9 −22.8 −0.8 b* 27.9 29.2 53.7 51.4 −22.3 39.4 Color Red Pink GreenLight green Blue Yellow 1064 nm Laser mark color L* 58.3 58.6 45.9 45.456.7 68.3 68.3 45.4 22.9 (mark) a* 57.9 35.4 −7.2 −4.2 −9.7 −2.2 57.9−9.7 67.5 b* 25.7 13.8 11.6 5.1 −9.4 16.2 25.7 −9.4 35.1 Color Red PinkGreen Light green Blue Yellow 355 nm Laser mark color L* 52.3 54.8 55.257.0 56.4 55.4 57.0 52.3 4.7 (mark) a* 10.0 8.3 −5.7 −3.1 −4.1 −0.1 10.0−5.7 15.8 b* 9.1 8.8 16.9 12.5 2.9 8.5 16.9 2.9 14.0 Color Red PinkGreen Light green Blue Yellow 1064 nm Laser mark color L* 40.4 37.4 34.436.6 37.1 44.3 44.3 34.4 9.9 (mark) a* A 27.8 15.1 −3.1 −1.8 −4.2 0.627.8 −4.2 32.0 b* C 11.6 7.3 7.0 6.9 −0.9 10.8 11.6 −0.9 12.5 Color RedPink Green Light green Blue Yellow 1064 nm (Rofin) L* 29.7 28.9 27.828.4 28.5 28.9 29.7 27.8 1.8 (mark) a* A 5.8 2.1 0.2 0.2 0.1 0.6 5.8 0.15.7 b* C 2.6 1.4 1.2 1.0 0.8 2.1 2.6 0.8 1.8 Color Red Pink Green Lightgreen Blue Yellow 355 nm Laser mark color L* A (x3) 31.5 32.0 31.8 32.633.2 32.6 33.2 31.5 1.8 (mark) a* C 1.6 1.4 −0.2 0.2 −0.2 0.4 1.6 −0.21.8 b* E 1.1 1.3 1.5 1.6 1.1 1.6 1.6 1.1 0.5 Color Red Pink Green Lightgreen Blue Yellow

TABLE 28 Spec Exc. Sample Construct 85 86 87 88 89 90 Max Min Spread1064 nm Laser mark color L* 53.8 54.7 46.0 40.2 52.7 64.8 64.8 40.2 24.6(mark) a* 63.3 40.0 −7.3 −5.3 −11.1 −2.3 63.3 −11.1 74.5 b* 30.5 16.411.5 6.9 −10.5 17.6 30.5 −10.5 41.0 Color 355 nm Laser mark color L*52.3 54.6 55.9 57.3 56.4 55.2 57.3 52.3 5.0 (mark) a* 10.3 8.6 −6.1 −3.2−4.2 −0.1 10.3 −6.1 16.4 b* 8.6 8.3 17.0 12.2 2.4 8.2 17.0 2.4 14.6Color 1064 nm Laser mark color L* 32.4 27.6 34.6 26.5 26.7 37.1 37.126.5 10.6 (mark) a* A 36.3 22.0 −3.2 −2.9 −6.5 0.8 36.3 −6.5 42.8 b* C17.6 12.3 7.3 12.6 −1.1 15.1 17.6 −1.1 18.7 Color 1064 nm (Rofin) L*15.2 12.0 12.6 12.6 11.5 13.3 15.2 11.5 3.7 (mark) a* A 11.2 5.1 0.1 0.30.1 1.2 11.2 0.1 11.2 b* C 5.4 3.6 1.0 1.8 1.7 4.7 5.4 1.0 4.4 Color RedPink Green Light green Blue Yellow 355 nm Laser mark color L* A x 3 17.418.3 18.7 19.3 20.8 19.5 20.8 17.4 3.4 (mark) a* C 3.2 2.5 −0.3 0.3 −0.30.6 3.2 −0.3 3.6 b* E 2.7 3.0 3.2 3.4 2.3 3.3 3.4 2.3 1.0 Color Red PinkGreen Light green Blue Yellow

TABLE 29 Construction Sample L* a* b* dL* da* db* dE Sample No. 96.0 0.00.5 65 PC Sample No. 91 94.3 1.5 4.0 −1.7 1.5 3.5 4.2 65 & BR Sample No.77.3 10.8 8.7 −17.0 9.4 4.7 20.0 65 & BR laser marked Sample No. 95.3−0.2 0.1 67 Sample No. 92 94.1 0.7 1.6 −1.2 0.8 1.5 2.1 67 & BR SampleNo. 81.1 8.7 5.8 −13.0 8.0 4.2 15.9 67 & UVA & BR laser marked SampleNo. 93 95.1 −0.8 −0.3 −0.8 −0.8 −0.8 1.4 65 & OB Sample No. 88.5 −4.1−6.0 −6.6 −3.3 −5.7 9.3 65 & OB laser marked

Table 29 lists various constructions illustrating the use ofphotochromic additives. BR and OB denote that the sample was impregnatedwith berry red or oxford blue (spirooxazine photochromic additives),respectively. FIG. 15 illustrates the use of photochromic additives insample Nos. 91 (left) and 93 (right).

Set forth below are some embodiments of the methods and articles.

Embodiment 1

An article for laser marking comprising: a thermoplastic compositioncomprising a thermoplastic polymer, an active component comprising atleast one of a polymeric unit and an additive, wherein the thermoplasticpolymer has a visible transmission of greater than or equal to 80%according to ASTM D1003-00, Procedure A, using D65 illumination, 10degrees observer, and thickness of 1 mm; a mark produced by chemicalrearrangement of the active component generated by a laser of a firstwavelength; wherein the mark exhibits at least one of: (i) a change inoptical properties in the region 400 nm to 700 nm when exposed to lighthaving a wavelength less than or equal to 500 nm; and (ii) a change inoptical properties in the region of 400 nm to 700 nm when exposed tolight having a wavelength greater than or equal to the first wavelength.

Embodiment 2

The article of Claim 1, wherein the mark exhibits a change in opticalproperties in the region 400 nm to 700 nm when exposed to light having awavelength less than or equal to 400 nm.

Embodiment 3

The article of any of Claims 1 to 2, wherein the mark is visible whenexposed to light having a wavelength of less than or equal to 400 nm.

Embodiment 4

The article of Claim 3, wherein the mark is only visible when exposed tolight having a wavelength of less than or equal to 400 nm.

Embodiment 5

The article of any of Claims 1 to 4, wherein the thermoplasticcomposition comprises another additive comprising at least one ofultraviolet absorbing additive selected from hydroxybenzophenones,hydroxybenzotriazoles, hydroxybenzotriazines, cyanoacrylates,oxanilides, benzoxazinones, benzylidene malonates, hindered amine lightstabilizers, nano-scale inorganics, and combinations comprising at leastone of the foregoing.

Embodiment 6

The article of any of Claims 1-5, wherein the active component has estergroups of the formula

wherein at least 60 percent of the total number of R¹ groups containaromatic moieties and the balance thereof are aliphatic, alicyclic, oraromatic, and R² groups can be oxygen, aliphatic, alicyclic, oraromatic, or contain aromatic moieties with the balance thereof beingaliphatic, alicyclic, or aromatic.

Embodiment 7

The article of Claim 6, wherein the active component is a carbonategroup, R² is oxygen derived.

Embodiment 8

The article of any of Claims 1-7, comprising the additive, wherein theadditive is photochromic.

Embodiment 9

The article of any of Claims 1-8, comprising the additive, wherein theadditive is spiropyran, spirooxazine, fulgide, diarylethene,spirodihydroindolizine, azo-compounds, and Schiff base family,benzo-family, naphthopyrans family, or a combination comprising at leastone of the foregoing.

Embodiment 10

The article of any of Claims 1-9, wherein the thermoplastic polymer hasless than or equal to 50% carbonate groups.

Embodiment 11

The article of any of Claims 1-9, wherein the thermoplastic polymercomprises polycarbonate, polyesters, polymethyl methacrylate,polystyrene, polybutylene terephthalate, polyolefins, polyamides,polyvinylchloride, polylactic acid, and combinations comprising at leastone of the foregoing.

Embodiment 12

The article of any of Claims 1-11, wherein the thermoplastic polymercomprises a polycarbonate copolymer.

Embodiment 13

The article of any of Claims 1-12, wherein the polycarbonate copolymeris a polyester-carbonate copolymer.

Embodiment 14

The article of any of Claims 1-13, wherein the change in opticalproperties comprises a change in reflection.

Embodiment 15

The article of any of Claims 1-13, wherein the change in opticalproperties comprises a change in absorption.

Embodiment 16

The article of any of Claims 1-15, wherein the first wavelength is lessthan or equal to 500 nm.

Embodiment 17

The article of any of Claims 1-16, wherein the first wavelength is lessthan or equal to 400 nm.

Embodiment 18

A multilayered article for laser marking comprising: a first layerhaving a visible transmission of greater than or equal to 80% accordingto ASTM D1003-00, Procedure A, using D65 illumination, 10 degreesobserver, at a thickness of the first layer in the multilayer article; asecond layer having a visible transmission of greater than or equal to80% according to ASTM D1003-00, Procedure A, using D65 illumination, 10degrees observer, at a thickness of the second layer in the multilayerarticle, and wherein the second layer comprises a component that willform a laser mark with an L* of less than or equal to 40 as measuredaccording to CIELAB 1976 (specular included), when exposed to a laserlight of a wavelength of greater than 800 nm; a third layer reflectiveto laser light having a wavelength greater than 800 nm, wherein thethird layer has a visible transmission of greater than or equal to 80%according to ASTM D1003-00, Procedure A, using D65 illumination, 10degrees observer, at a thickness of the third layer in the multilayerarticle; and optionally a substrate; wherein the article comprises alaser mark having an L* of less than or equal to 40 as measuredaccording to CIELAB 1976 (specular included).

Embodiment 19

The article of Claim 18, wherein each of the first layer, second layerand the third layer, independently, comprise a thickness 25 to 500micrometers.

Embodiment 20

The article of Claim 19, wherein the thickness is 25 to 300 micrometers.

Embodiment 21

The article of Claim 20, wherein the thickness is 25 to 200 micrometers.

Embodiment 22

The article of any of Claims 18 to 21, wherein the article includes asubstrate comprising a visible transmission of less than or equal to 10%according to ASTM D1003-00, Procedure A, using D65 illumination, 10degrees observer, at a thickness of 1 mm.

Embodiment 23

The article of any of Claims 18 to 22, wherein the article includes thesubstrate, wherein the substrate has a substrate thickness of greaterthan 500 micrometers.

Embodiment 24

The article of any of Claims 18 to 23, wherein the article includes thesubstrate, and wherein the substrate is a non-white substrate.

Embodiment 25

A multilayered article for laser marking comprising: a first layerhaving a visible transmission of greater than or equal to 80% accordingto ASTM D1003-00, Procedure A, using D65 illumination, 10 degreesobserver, at a thickness of the first layer in the multilayer article; asecond layer having a visible transmission of greater than or equal to80% according to ASTM D1003-00, Procedure A, using D65 illumination, 10degrees observer, at a thickness of the second layer in the multilayerarticle, and wherein the second layer comprises an active component thatwill form a laser mark with an L* of less than or equal to 40 asmeasured according to CIELAB 1976 (specular included), when exposed to alaser light of a wavelength of greater than 800 nm; and a non-whitesubstrate.

Embodiment 26

The article of Claim 25, wherein non-white comprises dE of greater than10 compared with a RAL 9010 background.

Embodiment 27

The article of any of Claims 25 to 26, wherein non-white comprises dE ofgreater than 20 compared with a RAL 9010 background.

Embodiment 28

The article of any of Claims 18 to 27, comprising the substrate having avisible transmission of less than or equal to 10% according to ASTMD1003-00, Procedure A, using D65 illumination, 10 degrees observer, at athickness of 1 mm.

Embodiment 29

A multilayered article, comprising: a first layer having a visibletransmission of greater than or equal to 80% according to ASTM D1003-00,Procedure A, using D65 illumination, 10 degrees observer, at a thicknessof the first layer in the multilayer article; and a second layer, activeto laser light having a wavelength less than or equal to 500 nm, whereinthe second layer is active via an active component that will form alaser mark with an L* of less than or equal to 40 when exposed to alaser light of a wavelength of less than or equal to 500 nm; wherein thearticle comprises a laser mark having a mark L* less than or equal to40, as measured according to CIELAB 1976 (specular included).

Embodiment 30

The article of any of Claims 18 to 29, wherein the article comprises alaser mark having an L* of less than or equal to 35 as measuredaccording to CIELAB 1976 (specular included).

Embodiment 31

The article of any of Claims 18 to 30, wherein the article comprises alaser mark having an L* of less than or equal to 25 as measuredaccording to CIELAB 1976 (specular excluded).

Embodiment 32

The article of any of Claims 18 to 31, wherein the second layercomprises less than or equal to 500 ppm of a UV absorbing additive.

Embodiment 33

The article of any of Claims 18 to 32, wherein the second layercomprises less than or equal to 200 ppm of a UV absorbing additive.

Embodiment 34

The article of any of Claims 18 to 33, wherein the second layercomprises less than or equal to 100 ppm of a UV absorbing additive.

Embodiment 35

The article of any of Claims 23 to 34, further comprising a third layerhaving a transmission of less than 30% at the laser wavelength accordingto ASTM D1003-00, Procedure A, using D65 illumination, 10 degreesobserver, at a thickness of the third layer in the article.

Embodiment 36

The article of Claim 35, wherein the third layer has a transmission ofless than 10% at the laser wavelength according to ASTM D1003-00,Procedure A, using D65 illumination, 10 degrees observer, at a thicknessof the third layer in the article.

Embodiment 37

The article of any of Claims 18-36, wherein the substrate comprisesthermoplastic polymer, and wherein the thermoplastic polymer has avisible transmission of greater than or equal to 70% according to ASTMD1003-00, Procedure A, using D65 illumination, 10 degrees observer, andthickness of 1 mm.

Embodiment 38

The article of any of Claims 18-37, wherein the thermoplastic polymerhas a visible transmission of greater than or equal to 80% according toASTM D1003-00, Procedure A, using D65 illumination, 10 degrees observer,and thickness of 1 mm.

Embodiment 39

The article of any of Claims 37 to 38, wherein the article furthercomprises a white mark.

Embodiment 40

The article of any of Claims 37 to 39, wherein the laser mark is capableof fluorescing.

Embodiment 41

A method of inscribing a substrate, comprising: contacting the substratewith a laser beam to generate a laser mark, wherein the mark resultsfrom increasing the reflectivity of the thermoplastic material, whereinthe substrate comprises a composition comprising a non-reflectivethermoplastic material.

Embodiment 42

The method of Claim 41, wherein the composition comprises anon-reflective thermoplastic material capable of absorbing light havinga wavelength of less than or equal to 500 nanometers.

Embodiment 43

The method of any of Claims 41 to 42, wherein the composition furthercomprises an ultraviolet absorbing additive capable of absorbing lighthaving a wavelength of less than or equal to 500 nanometers.

Embodiment 44

The method of Claim 43, wherein the ultraviolet absorbing additive isselected from hydroxybenzophenones, hydroxybenzotriazoles,hydroxybenzotriazines, cyanoacrylates, oxanilides, benzoxazinones,benzylidene malonates, hindered amine light stabilizers, nano-scaleinorganics, and combinations comprising at least one of the foregoing.

Embodiment 45

The method of any of Claims 41 to 44, wherein the substrate has amaximum reflection in the visible spectrum represented by an L* value ofless than 25 when measured with a black background according to ASTME308-08 and CIELAB 1976 (specular included).

Embodiment 46

The method of any of Claims 41 to 45, wherein the L* value is less than20 (specular included).

Embodiment 47

The method of any of Claims 41 to 46, wherein the substrate isun-pigmented.

Embodiment 48

The method of any of Claims 41 to 47, wherein the laser beam has awavelength less than or equal to 500 nanometers.

Embodiment 49

The method of any of Claims 41 to 48, wherein the mark is a watermark.

Embodiment 50

The method of any of Claims 41 to 49, wherein the watermark has aprofile height of less than 15 micrometers.

Embodiment 51

The method of any of Claims 41 to 50, wherein the profile height is lessthan 10 micrometers.

Embodiment 52

The method of any of Claims 41 to 48, wherein the mark is a lightcolored mark.

Embodiment 53

The method of Claim 52, wherein the light colored mark has a profileheight of less than 35 micrometers.

Embodiment 54

The method of Claim 53, wherein the profile height is less than 30micrometers.

Embodiment 55

The method of any of Claims 41 to 54, wherein the composition iscolored.

Embodiment 56

The method of any of Claims 41 to 55, wherein the mark is a white mark.

Embodiment 57

The method of any of Claims 41 to 56, wherein the composition is furtherinscribed with a laser beam having a wavelength greater than 500 nm toachieve a dark mark.

Embodiment 58

The method of any of Claims 41 to 57, wherein the substrate has avisible transmission of greater than 70% as measured according to ASTMD1003-00, Procedure A, using D65 illumination, 10 degrees observer, andthickness of 1 mm.

Embodiment 59

The method of Claim 58, wherein the visible transmission is greater than75%.

Embodiment 60

The method of any of Claims 54 to 59, wherein the visible transmissionis greater than 80%.

Embodiment 61

The method of any of Claims 41 to 60, wherein the composition comprisesa material selected from the group consisting of polycarbonate,polycarbonate copolymers, polyester, polymethyl methacrylate,polystyrene, polyamide, polyolefin, polyvinyl chloride, polyimide,polyetherimide, polylactic acid, and combinations comprising at leastone of the foregoing.

Embodiment 62

The method of any of Claims 41 to 61, wherein the mark has an increasein L* of greater than or equal to 20 compared to the thermoplasticmaterial.

Embodiment 63

The method of any of Claims 41 to 62, wherein the mark has an increasein L* of greater than or equal to 25 compared to the thermoplasticmaterial.

Embodiment 64

The method of any of Claims 41 to 63, wherein the mark comprisesindividual laser inscribed dots having a diameter of less than or equalto 80 micrometers.

Embodiment 65

The method of Claim 64, wherein the diameter is less than or equal to 60micrometers.

Embodiment 66

The method of any of Claims 64 to 65, wherein the diameter is less thanor equal to 40 micrometers.

Embodiment 67

The method of any of Claims 41 to 48 and 52-66, wherein the mark has areflection greater than 15% in a marked side of the article and wherethe reflection from the opposite side is more than half that on themarked side (for example, the marked side of the article is the sidecontacted by the laser that forms the laser mark).

Embodiment 68

A method of attaching a first component to a second component,comprising: contacting a first component comprising a first componentcomposition and a second component comprising a second componentcomposition with an ultraviolet laser beam having a wavelength less thanor equal to 500 nanometers, wherein the first component compositioncomprises a non-reflective thermoplastic material that is transparent tolaser light having a wavelength less than or equal to 500 nanometers andwherein the second component composition comprises a non-reflectivethermoplastic material capable of absorbing light having a wavelengthless than or equal to 500 nanometers; and generating an interactionbetween the first component and the second component to attach the firstcomponent to the second component.

Embodiment 69

The method of Claim 68, further comprising generating a mark on thesecond component.

Embodiment 70

A method for generating a mark on an article, comprising: bonding afirst component to a second component with a laser beam having awavelength of greater than or equal to 800 nanometers, wherein the firstcomponent composition comprises a thermoplastic composition absorbinglight having a wavelength of less than or equal to 500 nanometers andwherein the second component comprises a thermoplastic compositionabsorbing light having a wavelength of greater than or equal to 800nanometers.

Embodiment 71

An article formed by the method of any of Claims 41 to 70.

Embodiment 72

The article of any of Claims 1-40 and 70, wherein the article comprisesan authentication identifier on an identification document, athermoplastic glazing, a business card, a gift card, a ticket, anelectronic housing, a television bezel, optical glassware, andcombinations comprising at least one of the foregoing.

Embodiment 73

A method of making a consistent black mark (having an L* less than orequal to 40, as measured according to CIELAB 1976 (specular included)),in an article, comprising: decoupling an active component from asubstrate, locating the active component in a layer between thesubstrate and an outer layer (also referred to herein as a first layer),wherein the outer layer has a visible transmission of greater than orequal to 80% according to ASTM D1003-00, Procedure A, using D65illumination, 10 degrees observer, at a thickness of the first layer inthe multilayer article; contacting the active component with a laserlight to form a mark having an L* of less than or equal to 40 asmeasured according to CIELAB 1976 (specular included).

Embodiment 74

The method of Embodiment 73, wherein the substrate has a color (e.g.,the substrate is not white or black).

Embodiment 75

The method of any of Embodiments 73-74, wherein the laser light has awavelength of less than or equal to 500 nm.

Embodiment 76

The method of any of Embodiments 73-75, wherein the laser light has awavelength of less than or equal to 400 nm.

Embodiment 77

The method of any of Embodiments 73-74, wherein the laser light has awavelength of greater than or equal to 800 nm.

Embodiment 78

The method of any of Embodiments 73-77, wherein the mark is produced bychemical rearrangement.

Embodiment 79

The method of any of Embodiments 73-78, wherein the mark is capable offluorescing.

Embodiment 80

The article of any of Claims 1-15, wherein the article is monolithic.

Embodiment 81

The article of any of Claims 1-15, wherein the article is one layeronly, not multilayered.

All ranges disclosed herein are inclusive of the endpoints, and theendpoints are independently combinable with each other (e.g., ranges of“up to 25 wt. %, or, more specifically, 5 wt. % to 20 wt. %”, isinclusive of the endpoints and all intermediate values of the ranges of“5 wt. % to 25 wt. %,” etc.). “Combination” is inclusive of blends,mixtures, alloys, reaction products, and the like. Furthermore, theterms “first,” “second,” and the like, herein do not denote any order,quantity, or importance, but rather are used to differentiate oneelement from another. The terms “a” and “an” and “the” herein do notdenote a limitation of quantity, and are to be construed to cover boththe singular and the plural, unless otherwise indicated herein orclearly contradicted by context. The suffix “(s)” as used herein isintended to include both the singular and the plural of the term that itmodifies, thereby including one or more of that term (e.g., the film(s)includes one or more films). Reference throughout the specification to“one embodiment”, “another embodiment”, “an embodiment”, and so forth,means that a particular element (e.g., feature, structure, and/orcharacteristic) described in connection with the embodiment is includedin at least one embodiment described herein, and may or may not bepresent in other embodiments. “Optional” or “optionally” means that thesubsequently described event or circumstance can or cannot occur, andthat the description includes instances where the event occurs andinstances where it does not.

Compounds are described using standard nomenclature. For example, anyposition not substituted by any indicated group is understood to haveits valency filled by a bond as indicated, or a hydrogen atom. A dash(“-”) that is not between two letters or symbols is used to indicate apoint of attachment for a substituent. For example, —CHO is attachedthrough carbon of the carbonyl group. In addition, it is to beunderstood that the described elements may be combined in any suitablemanner in the various embodiments.

All cited patents, patent applications, and other references areincorporated herein by reference in their entirety. However, if a termin the present application contradicts or conflicts with a term in theincorporated reference, the term from the present application takesprecedence over the conflicting term from the incorporated reference.

While particular embodiments have been described, alternatives,modifications, variations, improvements, and substantial equivalentsthat are or may be presently unforeseen may arise to applicants orothers skilled in the art. Accordingly, the appended claims as filed andas they may be amended are intended to embrace all such alternatives,modifications variations, improvements, and substantial equivalents.

What is claimed is:
 1. An article, comprising: a layer E including alight mark and comprising a thermoplastic composition capable ofabsorbing light having a wavelength less than or equal to 500nanometers, wherein layer E has a front side and a rear side; whereinthe light mark was formed by contacting the front side of the layer Ewith a laser light having a wavelength of less than or equal to 500nanometers; wherein the light mark resulted from an increase inreflectivity of the thermoplastic composition contacted by the laserlight; wherein the layer E has a visible transmission of greater than orequal to 80% according to ASTM D1003-00, Procedure A, using D65illumination, 10 degrees observer, and at a thickness of 1 mm; whereinwhen measuring the light mark from the front side, the light markmeasured from the front side has a front side mark L* measured accordingto CIELAB 1976 (specular included); wherein when measuring the lightmark from the rear side, the light mark measured from the rear side hasa rear side mark L* measured according to CIELAB 1976 (specularincluded) and a rear side average percent reflection of 11.5 to 25.3 asmeasured according to ASTM D1003-00 using D65 illumination and 10degrees observer at a thickness of 1 mm; and wherein a delta between thefront side mark L* and the rear side mark L* is 1 to
 10. 2. The articleof claim 1, further comprising a layer C having a visible transmissionof greater than or equal to 80% according to ASTM D1003-00, Procedure A,using D65 illumination, 10 degrees observer, at a thickness of the layerC in the multilayer article, wherein the layer C has a dark laser mark;wherein the layer C comprises an additive that will form the dark lasermark with an L* of less than or equal to 40 as measured according toCIELAB 1976 (specular included); and wherein the dark laser mark wasformed by contacting the layer C, through layer E, with a laser lighthaving a wavelength of greater than 800 nm.
 3. The article of claim 2,wherein the layer C comprises an additive, and wherein the additivecomprises at least one of carbon black, a nano-scale inorganic, and ametal oxide.
 4. The article of claim 2, further comprising a substratecomprising a dE of greater than 10 compared with a RAL 9010 background,wherein the layer C is between the substrate and the layer E.
 5. Thearticle of claim 1, further comprising a layer A having a visibletransmission of greater than or equal to 80% according to ASTM D1003-00,Procedure A, using D65 illumination, 10 degrees observer, at a thicknessof the layer A in the article; and a layer C, wherein the layer C has adark laser mark, and wherein the layer C comprises an additive that willform the dark laser mark when contacted with a laser light having awavelength of less than 500 nm; wherein the layer C has a visibletransmission of greater than or equal to 80% according to ASTM D1003-00,Procedure A, using D65 illumination, 10 degrees observer, at a thicknessof the layer C in the article; wherein the dark laser mark that wasformed when the layer C was contacted, through the layer A, with a laserlight having a wavelength of less than 500 nm; wherein the dark lasermark has an L* of less than or equal to 40 as measured according toCIELAB 1976 (specular included); and wherein the layer C is between thelayer E and the layer A.
 6. The article of claim 5, wherein the additivecomprises at least one of carbon black, a nano-scale inorganic, metaloxide.
 7. The article of claim 6, wherein the layer C comprises lessthan or equal to 500 ppm of the additive.
 8. The article of claim 6,wherein the additive comprises at least one of lanthanum hexaboride andcesium tungsten oxide.
 9. The article of claim 1, wherein the light markis a watermark.
 10. The article of claim 1, wherein the layer E furthercomprises at least one ultraviolet absorbing component selected fromhydroxybenzophenones, hydroxybenzotriazoles, hydroxybenzotriazines,cyanoacrylates, oxanilides, benzoxazinones, benzylidene malonates, andhindered amine light stabilizers, and nano-scale inorganics.
 11. Thearticle of claim 1, further comprising a layer A having a visibletransmission of greater than or equal to 80% according to ASTM D1003-00,Procedure A, using D65 illumination, 10 degrees observer, at a thicknessof the layer A in the article; and a dark laser mark having an L* ofless than or equal to 40 as measured according to CIELAB 1976 (specularincluded); wherein the dark laser mark was formed by contacting thelayer E, through the layer A, with a laser light having a wavelength ofgreater than 800 nm; and wherein the layer E comprises at least oneadditive selected from carbon black, a nano-scale inorganic, and metaloxide.
 12. The article of claim 11, wherein the layer E furthercomprises at least one ultraviolet absorbing component selected fromhydroxybenzophenones, hydroxybenzotriazoles, hydroxybenzotriazines,cyanoacrylates, oxanilides, benzoxazinones, benzylidene malonates,hindered amine light stabilizers, and nano-scale inorganics.
 13. Thearticle of claim 1, wherein the light mark comprises individual laserinscribed microdots having a diameter of less than or equal to 80micrometers.
 14. The article of claim 1, wherein the light mark is a UVfluorescent mark that is a result of a change in optical properties inthe region 400 nm to 700 nm when exposed to light having a wavelengthless than or equal to 500 nm.
 15. The article of claim 1, wherein thearticle comprises an authentication identifier on an identificationdocument, a thermoplastic glazing, a business card, a gift card, aticket, an electronic housing, a television bezel, optical glassware.16. The article of claim 1, wherein the article is selected from aglazing part, pharmaceutical packaging, food packaging, electronichousing, electronic screen, eyewear lens, eyewear frame, card, andticket.
 17. A method of forming an article with a dark laser mark and alight mark, comprising: locating a layer C between a layer E and a layerA; and directing a laser light having a wavelength of less than or equalto 500 nanometers at a layer E to increase reflectivity of an areacontacted by the laser light and to form the light mark; and forming thedark laser mark in layer C, wherein the dark laser mark has an L* ofless than or equal to 40 as measured according to CIELAB 1976 (specularincluded); wherein the layer A has a visible transmission of greaterthan or equal to 80% according to ASTM D1003-00, Procedure A, using D65illumination, 10 degrees observer, at a thickness of the layer A in thearticle; wherein the layer E comprises a thermoplastic compositioncapable of absorbing light having a wavelength less than or equal to 500nanometers; and has a visible transmission of greater than or equal to80% according to ASTM D1003-00, Procedure A, using D65 illumination, 10degrees observer, and at a thickness of 1 mm; wherein when measuring thelight mark from the front side, the light mark measured from the frontside has a front side mark L* measured according to CIELAB 1976(specular included); wherein when measuring the light mark from the rearside, the light mark measured from the rear side has a rear side mark L*measured according to CIELAB 1976 (specular included) and a rear sideaverage percent reflection of 11.5 to 25.3 as measured according to ASTMD1003-00 using D65 illumination and 10 degrees observer at a thicknessof 1 mm; and wherein a delta between the front side mark L* and the rearside mark L* is 1 to
 10. 18. The article of claim 1, wherein the rearside average percent reflection is 14.7 to 25.3.
 19. The article ofclaim 1, wherein the delta between the front side mark L* and the rearside mark L* is 1 to 8.